Commission of the European Communities

PHOSPHORUS IN SEWAGE SLUDGE AND ANIMAL WASTE SLURRIES

Proceedings of the EEC Seminar organized jointly by the CEC and the Institute for Soil Fertility, Haren (Gr.) and held in Groningen, Netherlands on June 12 and 13, 1980.

Sponsored by the Commission of the European Communities, Directorate-General for Agriculture and Directorate-General for Research, Science and Education

Edited by

T. W. G.HUCKER
Department of the Environment, London, United Kingdom and

G.CATROUX
' Ministere de I'Agriculture, INRA, Laboratoire de Microbiologie des Sols, Dijon, France

PARL EUROP . Biblioth. N. C. Com.

D. REIDEL PUBLISHING COMPANY
DORDRECHT : HOLLAND / BOSTON : U.S.A. LONDON : ENGLAND

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Library of Congress Cataloging in Publication Data Main entry under title: Phosphorus in sewage sludge and animal waste slurries. 1. SoilsPhosphorus contentCongresses. 2. PhosphorusEnviron mental aspectsCongresses. 3. Sewage sludgeCongresses. 4. Animal wasteCongresses. I . Hucker, T. W. G., 1 9 2 2 . II . Catroux, G., 1938 I I I . Commission of the European Communities. I V. I nstituut voor Bodemvruchtbaarheid (Netherlands) S592.6.P5P47 628.36 81797 AACR2 ISBN 9027703175

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Publication arranged by Commission of the European Communities, gctorateG^neral I nformation Market and I nnovation, Luxembourg EUR711J Cop^jigtit 1981 ECSC, EEC, EAEC, Brussels and Luxembourg, 1981 Proceedings prepared by Janssen Services, 14 The Quay, Lower Thames Street, London EC3R 6BU LEGAL NOTI CE Neither the Commission of the European Communities nor any person acting on behalf of the Commission is responsible for the use which might be made of the following information. jf ^

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TABLE OF CONTENTS Preface Opening Remarks .. .. .. .. .. .. vii 1

SESSION I: GENERAL ASPECTS OF THE PHOSPHORUS CYCLE IN SOILS PHOSPHORUS IN RELATION TO WATER QUALITY: GREAT LAKES WATER QUALITY AND THE PHOSPHORUS REMOVAL PROGRAMME M.D. Webber .. .. .. PATHWAYS OF PHOSPHORUS IN SOIL R.E. White .. .. .. DISCUSSION .. .. .. LONG TERM PHOSPHATE BINDING CAPACITY OF SOME SOILS W.H. van Riemsdijk and F.A.M. da Haan .. PHOSPHORUS ANALYSIS IN SOILS A. Cottenie and L. Kiekens DISCUSSION .. .. .. .. ..

5 21 45 47 71 87

SESSION II: PHOSPHORUS IN WASTES (CONTENTS, CHEMICAL FORMS, ETC.) PHOSPHORUS CONTENT OF SLUDGE FROM SWISS SEWAGE TREATMENT PLANTS O.J. Furrer and R. Bolliger .. DISCUSSION .. ..

.. ..

91 98

THE CONTENT.OF PHOSPHORUS IN THE SLUDGE OF WALLONIAN WATER-PURIFICATION PLANTS AND THE FORM OF PHOSPHORUS IN THESE G. Hanotiaux, J.-P. Heck, M. Rocher, L. Barideau and 0. Marlier-Geets .. DISCUSSION'"' .. ..

.. ... .. ..

99 108 109 H8

PHOSPHORUS IN SEWAGE SLUDGE IN FINLAND I. Koskela .. .. DISCUSSION .. ..

INFLUENCE OF NUTRITIONAL AND PHYSIOLOGICAL FACTORS ON PHOSPHORUS CONTENT OF ANIMAL MANURES P.C.M. Simons and A.W. Jongbloed . . . DISCUSSION .. .. ..

119 132

SESSION III: PHOSPHORUS VALUE OF WASTES PHOSPHORUS VALUE OF SLUDGES RELATED TO THEIR METAL CONTENT B. Pommel .. .. DISCUSSION .. ..

.. ..

137 148

SEWAGE SLUDGE AS A PHOSPHATE FERTILISER S. de Haan .. .. DISCUSSION .. ..

.. ..

149 162

EFFECTS OF SLUDGE PROC ESSING ON SOIL PHOSPHORUS MOBILITY MEASURED WITH THE ISOTOPIC KINETIC S METHOD J.L. Morel .. .. .. DISCUSSION .. .. ..

163 175

AVAILABILITY OF PHOSPHORUS FRAC TIONS IN SEWAGE SLUDGE H. H3ni, S.K. Gupta and O.J. Furrer DISCUSSION .. ..

.. ..

177 189

PHOSPHORUS PROBLEMS AND SEWAGE SLUDGE APPLICATION IN AGRICULTURE A. SUss .. .. DISCUSSION .. ..

.. ..

191 202

PHOSPHORUS EFFEC T OF ANIMAL MANURE AND SEWAGE SLUDGE K.E. Larsen .. .. DISCUSSION .. ..

.. ..

207 229

SESSION IV: ACCUMULATION AND TRANSPORT OF PHOSPHORUS AFTER LANDSPREADING OF SLUDGES AND SLURRIES ACCUMULATION AND LEACHING OF PHOSPHORUS AS INFLUENCED BY SLUDGE APPLICATION O.J. Furrer .. .. DISCUSSION .. ..

.. ..

235 240

EFFECT OF PHOSPHORUS IN SEWAGE SLUDGE ON PHOSPHORUS IN CROPS AND DRAINAGE WATER S. de Haan .. .. DISCUSSION .. . .

.. . .

241 253

PHOSPHORUS BALANCE AFTER THE APPLICATION OF SEWAGE SLUDGE H. Kick . . .. DISCUSSION .. .

..

255 272

ACCUMULATION OF PHOSPHORUS IN A SANDY LOAM SOIL FROM FARMYARD MANURE [FYM] AND SEWAGE SLUDGE A.E. Johnston .. .. DISCUSSION .. ..

.. ..

273 286

PHOSPHORUS IN SEWAGE SLUDGE AND IT'S BEHAVIOUR IN SOIL J.H. Williams and E.G. Coker .. DISCUSSION .. ..

.. ..

291 308

PHOSPHORUS ACCUMULATION IN SOIL PROFILES AND PHOSPHORUS LOSSES AFTER THE APPLICATION DF ANIMAL MANURES H. Vetter and G. Steffens .. DISCUSSION .. ..

.. ..

309 328

PHOSPHORUS ACCUMULATION AND MOBILITY FROM LARGE APPLICATIONS OF SLURRY R.J. Unwin .. .. DISCUSSION .. ..

.. ..

333 345

MOBILITY OF PHOSPHORUS FROM PIG SLURRY IN SOILS R.G. Gerritse .. .. DISCUSSION .. ..

.. ..

347 367

THE EFFECT OF VERY INTENSIVE DRESSINGS OF LIVESTOCK EFFLUENT ON PHOSPHORUS IN SOIL J.P. Destain .. .. PROBLEMS RELATED TO PHOSPHORUS IN THE DISPOSAL OF SLURRY J.S.V. McAllister and R.J. Stevens DISCUSSION .. ..

..

371

.. ..

383 397

EVOLUTION OF PHOSPHORUS IN SEWAGE SLUDGE AFTER ITS APPLICATION TO THE SOIL G. Hanotiaux, J.P. Heck, M. Rocher, L. Barideau and 0. Marler-Geets .. DISCUSSION FINAL SESSION FINAL DISCUSSION CLOSING REMARKS List of Participants .. .. .. .. .. .. .. ..

.. ..

399 411

.. .. ..

415 427 431

Index of Subjects

..

..

..

437

PREFACE Whilst phosphorus is well known as a valuable nutrient encouraging plant growth,excessive quantities resulting from the disposal of human and animal wastes at high rates can result in adverse agricultural effects and environmental nuisance in polluting rivers etc.

The effects of phosphorus have been considered by those studying the disposal of Effluents and Wastes from Agriculture and by those involved in the Concerted Action project on research into the Treatment and Use of Sewage Sludge. Since many of the aspects of phosphorus utilisation and disposal are common to both agricultural and human waste disposal it was decided to hold a joint seminar in Haren, Netherlands in June 1980.

This book contains the papers submitted to the meeting and summaries of the discussion. The conference was divided into 4 sessions. The first was in the

form of an introduction and devoted to the general aspects of the phosphorus cycle in soils and included the binding capacity and analytical problems. The second was devoted to the phosphorus content of sludges and slurries with reference to variations in the phosphorus content of sludges and the effects of feedstuffs on animal slurries. trials and laboratory studies. variety of soils. The third session dealt with the phosphorus value of sludges and slurries and included references to field The fourth and final session covered the accumulation and leaching of phosphorus after landspreading on a wide

The seminar was most effective in bringing together the various aspects of phosphorus utilisation and disposal and the variations in the phosphorus from the different sources. It is hoped that the scientific reports in this volume will encourage the maximum use of the nutrient value of phosphorus whilst avoiding any harm from excessive application.

OPENING REMARKS T.W.G. Hucker (UK) Good morning ladies and gentlemen. This seminar on Phosphorus and Animal Wastes is a joint meeting of the two Working Parties on the utilisation of sewage sludge - Working Party 4, dealing with manurial value and Working Party 5, dealing with environmental effects, together with the Effluents from Livestock Research Programme. We have always felt that there is much common ground in waste disposal as a whole and this is our first opportunity to get together. Dr. Sluijsmans, who is the Director of the Institute for Soil Fertility at Haren, would like to say a few words of welcome. C.M.J. Sluijsmans ( iletherlands) Thank you Mr. Hucker. Ladies and gentlemen, the Staff and Management of the Institute for Soil Fertility appreciate very much that the European Commission has decided to organise this meeting here in Groningen. We are very pleased to see so many of you here to participate in the discussions. It means that the work that is done at our Institute on sewage sludge and other wastes, is recognised as providing a significant contribution to the knowledge we are all aiming at. It appears that our representatives in the various working groups make a favourable impression on their colleagues. I would just like to say a few words about our Institute. You have seen that we have a modern building in which to work. We moved in in 19 68 but the Institute was founded in 1890. In another ten years there might well be a good reason for another international conference to celebrate our centenary. The staff of the Institute comprises about 120 people, including 30 to 35 university graduates. At least 10 of these research workers are engaged full or part time on waste problems. The Institute is spending 15% to 20% of its budget on waste problems - sewage sludge, compost, dredged sludge and animal wastes. We anticipate that this level will continue for the

next five years with the accent on the effect of those materials on crop quality with regard to human and animal health, and on the effects on soil quality and ground and surface water. Today and tomorrow the subject of your sessions will be phosphorus. Thanks to the widespread use of phosphate fertilisers for many years in this country, a temporary halt in phosphate application would not have a disastrous consequence. From long term experiments we know that omitting phosphate, even for a period of five to ten years, would not result in a yield depression of more than 10% for potatoes and 5% for cereals. Compared with nitrogen, phosphate can be regarded as much less important in this country. Nevertheless, together with our colleagues from abroad, we are continuing to study the remaining questions with regard to phosphate. It is our task to answer such questions as whether phosphate is leached to the surface water and how much time it takes to do this in different soil profiles; the run-off of phosphate; the availability in different fertilisers and wastes, and the effect of granulation of fertilisers and wastes, particularly understanding the effect of granulation. We must understand why one method of analysis of soil phosphate is better than another; why is analysis of phosphate in acid extract, for our grassland, better than in water? Why is water better than acid on arable land? We must discover why phosphate in one sewage works better than another. At our Institute we are happy to have so many colleagues from elsewhere who are actively working on these problems and who are willing to transmit their knowledge to us. You are all very welcome from that point of view also. T.W.G. Hucker Thank you Dr. Sluijsmans for those words of welcome and introduction. Having travelled the length of Holland in the past week I can say that the Institute for Soil Fertility can be seen to be doing an excellent job - the soil is certainly producing excellent crops. We all appreciate the atmosphere in which we have been received here and we are looking forward to the next two days.
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SESSION I GENERAL ASPECTS OF THE PHOSPHORUS CYCLE IN SOILS

Chairman: T.W.G. Hucker

3-

PHOSPHORUS IN RELATION TO WATER QUALITY: GREAT LAKES WATER QUALITY AND THE PHOSPHORUS REMOVAL PROGRAMME M.D. Webber Wastewater Technology Centre, Environmental Protection Service, Department of the Environment, Burlington, Ontario, L7R 4A6, Canada. ABSTRACT Phosphorus Great Lakes. 1 mg/l total charges. chemical phosphorus agricultural Joint is the main factor Canada/United loadings contributing initiatives to eutrophication have been objective to and industrial indiate that the on in the undertaken of disinclude

States

to reduce phosphorus In Ontario, addition removal land.

to the Lakes.. treatment removal.

An effluent

phosphorus

has been set for municipal wastewater Studies

has been upgraded

for phosphorus sludges

can be used successfully

as fertilisers

INTRODUCTION This paper outlines the effects of phosphorus on water quality. It discusses programmes undertaken to reduce phosphorus discharges from municipal and industrial sources to the Lower Great Lakes and summarises the results of studies on land application of phosphorus removal sludges. Phosphorus occurs universally in low concentrations in soil and water and is a major nutrient required by plants and animals. It is dispersed into the environment through a variety of mechanisms including municipal and industrial discharges, the spreading of commercial fertilisers, animal manures and sewage sludge and soil erosion. EFFECTS OF PHOSPHORUS ON WATER QUALITY It is now well established that phosphorus most commonly limits the yield in freshwater phytoplankton communities (Thomas et al., 1980). Substantial addition of phosphorus to a body of water usually results in increased algal productivity and increased decomposition of organic matter which causes depletion of oxygen. The animals also undergo profound shifts in abundance and the relative numbers of the different types. These changes are often referred to collectively as eutrophication. Several investigators have suggested that a concentration of 20 yg/1 total phosphorus in water in the spring may be used as an approximate lower limit of the condition where eutrophication is well advanced (eutrophy). They have also suggested that below 10 ug/1 few, if any, of the effects of eutrophication are evident. Such waters are in a nutrient-poor condition (oligotrophy). The intermediate or transitional state (mesotrophy) is defined as being between 10 and 20 pg/1.

Using these limits as guidelines, the present trophic status of the Great Lakes is summarised in Figure 1. Only Lakes Superior and Huron are safely in the oligotrophia state. Lake Michigan is approaching the mesotrophic state, while the Lower Lakes and Saginaw Bay must all be classified as eutrophic, although Lake Ontario and the central and eastern basins of Lake Erie are not yet strongly so.

SPRING TOTAL PHOSPHORUS l^g P/l)

c
SUPERIOR

10

20

30

tO

50

60

-J 1

MICHIGAN

HURON

1 II
1 '

SAGINAW BAY

-~>v r i

WESTERN ERIE

CENTRAL ERIE

EASTERN ERIE

ONTARIO

..'
OLCOTBCMT MISOTROPMT

! 1

Fig. 1. C urrent trophic status of the Great Lakes (Thomas et al., 1980) GREAT LAKES WATER QUALITY AGREEMENT ...

In 1969, the International Joint Commission reported to the Canadian and United States governments that transboundary water pollution was occurring to an extent that was causing injury to health and property on the other side of the boundary (Slater and Bangay, 1980). The report also identified a number of specific problems which required remedial action:

i r;:f.f vf'T

7-

1.

accelerated eutrophication of Lake Ontario and a condition of advanced eutrophication in the western basin of Lake Erie, largely as a result of increased nutrient inputs, especially phosphorus; a disruption of beneficial uses of water as a result of changing trophic conditions; dramatic changes in the species composition of commercial fish catches; pollution problems related to dredge spoil disposal; bacterial pollution of nearshore waters; and pollution from organic contaminants, spills of oil and other hazardous substances, radioactive materials, viral contamination and thermal pollution.

2.

3.

4. 5. 6.

A number of specific recommendations were made to deal with the problem of eutrophication including: 1. immediate reductions in the phosphorus content in detergents; implementation of programmes for the reduction of phosphorus from municipal and industrial waste effluents, including a timetable for reductions; the development of programmes for the control of phosphorus from agricultural operations; regulation of any new uses of phosphorus which could result in appreciable additions to the lakes.

2.

3.

4.

In recognition of the importance of these findings the two governments began negotiations which culminated in a new strategy for managing Great Lakes water quality. The Great

Lakes Water Quality Agreement signed April 15th, 19 72 committed the governments to a scheduled reduction in phosphorus discharges from municipal and industrial sources to the Lower Lakes and called for an effluent objective of 1 mg/1 total phosphorus. It also directed the IJC to undertake studies of water quality in the Upper Lakes and to provide information on the quantities and control of pollution from diffuse or nonpoint sources. A number of important steps have been taken to reduce phosphorus input to the Great Lakes. In Canada, immediate steps were taken to reduce the phosphorus content in laundry detergents. In 1970, levels were reduced to 8.5% P by weight, and in 1972 this was further reduced to 2.2% P. In the United States, the existence of eight separate state jurisdictions has resulted in a somewhat less rapid and uniform reduction in phosphorus in detergents; however, only Ohio and Pennsylvania still do not control this source. Important reductions have also been achieved at municipal sewage treatment plants. In Lake Erie, the point source load has been reduced from approximately 10 000 metric tons/yr in 1972-7 3 to 5 700 metric tons/yr in 1977, and is expected to be 2 100 metric tons/yr when all controls are in place to meet the 1 mg/1 phosphorus effluent limit. In Lake Ontario, direct point source discharges have been reduced from approximately 6 300 metric tons/yr in 1972-73 to 2 600 metric tons/yr in 1977, and are expected to be 1 500 metric tons/yr when all controls are in place to meet the 1 mg/1 phosphorus effluent limit. CANADA/ONTARIO AGREEMENT To implement and accelerate pollution control programmes the governments of Canada and Ontario in August 1971 signed an agreement that secured funding for a $250 million capital works programme aimed at upgrading sewage collection systems and treatment works, including the installation of phosphorus removal equipment (Black, 1980). An additional $6 million over a 5 year term of the agreement was provided for related research studies. This was later extended for an additional 2 year period and provided an additional $1 million in research funding.
-9-

Under this funding programme, the effectiveness of uminium sulphate, ferric chloride and lime as prime coagulants r use in existing sewage treatment facilities was evaluated, predictive methodology involving jar testing techniques was veloped, whereby selection could be made of the prime coulant best suited for phosphorus removal at a particular ant. Temporary full-scale treatability studies were then rried out at selected plants to confirm the jar testing produres and determine design and operational parameters. By December 31st, 1975 there were a total of 168 sewage eatment plants in Ontario with permanent phosphorus removal cilities in operation. By December 31st, 1977 this number d increased to 211, representing about 85% of the provincial tal sewage hydraulic capacity. OSPHORUS REMOVAL BY PRECIPITATION Alum, iron chloride and lime have proven effective for osphorus removal from wastewater. The main mechanism for moval is thought to be precipitate formation resulting from e reaction of aluminium, iron and calcium ions with orthoosphate ions. However, some polyphosphates and organic osphorus compounds are also removed by a combination of mplex reactions and sorption onto floe particles. A survey of Ontario wastewater treatment plants, where cords were kept prior to and following the installation of osphorus removal systems, was conducted (Schmidtke, 1980). erage results indicated that addition of alum or iron loride for phosphorus removal increased both the mass of lids and the volume of sludge produced (Table 1 ) . Few tario plants practise phosphorus removal using lime, and no bstantive data base exists for sludge quantity estimation.

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TABLE 1 SLUDGE PRODUCTION SUGGESTED DESIGN DATA Sludge Quantity System Conventional Primary Upgraded Primary Conventional AS" Upgraded A S b Based on Influent = 0.66 m b Primary + waste activated g ds pcd 77 109 113 145 pcd Volume % of influent 0.20 0.32 0.38 0.51 kg ds/10 3 m 3

120 170 172 217

g ds pcd = gram dry solids per capita per day

In general, sludges produced from phosphorus removal facilities were digested readily in existing anaerobic and aerobic digesters. Some initial operating problems were experienced; however, these related more to the increased sludge production than to the nature of the sludge itself. No inhibitory effect of phosphorus removal chemical has been experienced in digester operation. Phosphorus resolubilisation within the digester was insignificant in relation to the total plant loading regardless of the chemical used. Anaerobic digestion reduced sludge production from 77, 109, 113 and 145 g ds pcd (Table 1) to 41, 63, 64 and 86 g ds pcd respectively, for conventional and upgraded primary plants and conventional and upgraded activated sludge plants. LAND APPLICATION OF PHOSPHORUS REMOVAL SLUDGES Approximately one-third (50 000 metric tons/yr dry wt.) of the sludge produced in Ontario is applied to agricultural land. Since phosphorus removal employs chemical precipitation processes, considerable concern was expressed as to the acceptability of the resulting alum (Al), iron (Fe) and lime (Ca) sludges for land application. -n-

In 1973, field and greenhouse experiments with Al, Fe and Ca sludges were initiated at the University of Guelph and lysimeter experiments were initiated at the Wastewater Technology Centre (Webber et al., 1980). The main objectives of these studies were to determine the effects of sludge application on crop yield and quality and on groundwater quality. Sludge application rates for the studies were based.on total Kjeldahl nitrogen (TKN) loadings and ranged from 0 to 1 600 kg TKN/ha/yr. The high application rates supplied much more nitrogen and phosphorus than was required for crop growth. The largest phosphorus and metal loadings to lysimeters to the end of 1977 were 14 178, 7.4, 1 030, 320, 910, 300 and 740 kg/ha P, Cd, Zn, Cu, Ni, Pb and Cr respectively, and approximated the largest loadings to the field. CROP YIELD Similar results were obtained from the field and lysimeter experiments. The yields of bromegrass and maize grown in the field and of orchard grass and wheat grown in the lysimeters were as large, or larger, with sludge than with commercial fertiliser. There were no consistent differences between yields from the Al, Fe and Ca sludge treatments. There was no evidence of yield reduction from the highest rates of sludge application. The amounts of P added in sludge to the field experiments during 1973 to 1975 were in the order Fe-sludge > Al-sludge > Ca-sludge, but the NaHCO,-extractable soil P was in the order Ca-sludge > Fe-sludge > Al-sludge. Sodium bicarbonate-extractable P is usually a good index of plant-available P in Ontario soils. However, in these studies, plant uptake did not reflect quantitatively a tremendous build-up of extractable P with repeated applications of Ca-sludge.

12-

CROP QUALITY Nitrate-N concentrations larger than 3 mg/g in forage may be hazardous to livestock. The concentrations in orchard grass were not monitored on a regular basis; however, data available for 1978 indicated that they increased with increasing sludge application rate but did not exceed 2 mg/g. Concentrations in maize stover and bromegrass were generally less than 2 mg/g, but materials grown on the treatments receiving the highest rates of sludge exceeded 3 mg/g in 1975. A comparison of metal concentrations in crops grown on the sludge treatment supplying the largest amount of metal and on a commercial fertiliser treatment is presented in Figure 2. In general, sludge application caused small to moderate increases in the Cd, Zn, Cu and Ni contents of the crops. Large increases in the Cd and Zn contents of maize stover and in the Ni contents of grasses reflected the application of sludges containing unusually large amounts of these metals. With the exception of Ni in orchard grass and Zn and possibly Cd in maize stover, there was no evidence of increasing metal content in the crops with repeated sludge application. Sludge application exhibited no consistent effects on the Pb and Cr contents of the crops. A more detailed discussion of this information was presented by Webber et al. (19 80). GROUNDWATER QUALITY Both the field and lysimeter experiments indicated a potential for groundwater contamination with N0--N when sludge application was in excess of that necessary to supply the nitrogen requirement of the growing crop. Nitrate concentrations in leachates from lysimeters receiving high application rates of sludge consistently exceeded the 11 mg/1 maximum permissible concentration for drinking water and sometimes exceeded 100 mg/1.

13-

Orchard grass 0.8-.

Bromegrass

Wheat straw

Wheat grain

Corn stover

Corn gram

Orchard grass

Bromegrass

Wheat straw

Wheat grain

Corn stover

Corn grain

160 Al S ludge Treatment Al S ludge Treatment 120

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CO

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Year

Metal concentrations (yg/g) in crops grown on soils treated with sludge (total bar) and commercial fertiliser (hatched bar)

Total P concentrations in leachates collected from the lysimeter experiments exhibited no consistent differences with time or with increasing rates of sludge application. However, periodic large concentrations have been observed (Figure 3) and the author is unable to offer an explanation for their occurrence. The concentrations for all sludge treatments were less than the 0.1 mg/1 detection limit'for P throughout 1973, 1974 and up to August 1975. Following August of both 1975 and 1976, concentrations for all treatments including the controls ranged from 1 to 2 mg/1 and early in 1977 they ranged as high as 13 mg/1. Since September of 1977 the concentrations have seldom exceeded 0.5 mg/1 and usually have been less than the detection limit. Late in 1976 one lysimeter from each treatment was sacrificed and soil samples were taken at narrow intervals down the profile. Analysis indicated that there had been little downward movement of P beyond 5 cm into the soil. Most of the added P was associated with the sludge cake and surface 1 cm of soil (Table 2 ) .
TABLE 2 TOTAL P CONCENTRATIONS (Pg/g) IN CONTROL AND SLUDGE TREATED LOAM SOIL TAKEN FROM LYSIMETERS Depth (cm) Surface 1 - 5 5-10 10 - 15 20 - 26 No treatment 600 798 739 637 560 NPK fertiliser 1 234 756 754 715 680 Alsludge 21 560 2 080 918 600 439 Fesludge 7 508 913 519 794 635 Casludge 6 970 1 064 840 760 677

Metal concentrations in the leachates were well within drinking water standards and except possibly for Zn and Cu did not increase with increasing rates of sludge application (Table 3).

10.09.0Iron Sludge 8.0 7.0 Lime Sludge 6.0 3 O) E 5.0 Q.

Alum Sludge

-O3.0
NPK Control

2.0-

1.0 0.0
MAY JUNE JULY AUG. S EPT. MAR. APR. MAY JUNE JULY AUG. S EPT. OCT. 'MAR.'APR.' MAY 'JUNE 'JULY' AUG.'S EPT OCT.
b

1976

1977

1978

Fig. 3.

Total P concentrations in leachates f rom the NPK control treatment and the high application rates of alum, iron and lime sludges.

TABLE 3 AVERAGE METAL CONCENTRATIONS LYSIMETERS (mg/1) IN 1 9 7 6 LEACHATES FROM LOAM SOIL IN

Treatment NPK fertiliser All sludge rates High sludge rates Drinking water*

Cd O.OOl O.OOl O.OOl O.Ol

Zn 0.018 0.032 0.044 5

Cu 0.016 0.019 0.026 1

Ni 0.007 0.008 0.010

Pb 0.005 0.008 0.007 0.05

Cr 0.007 0.006 0.007 0.05

* Maximum p e r m i s s i b l e c o n c e n t r a t i o n s defined i n Canada for d r i n k i n g water

Measurements i n d i c a t e d t h a t v i r t u a l l y a l l of t h e added metal was associated with the sludge cake and surface 1 cm of s o i l (Table 4 ) .

17-

TABLE 4 TOTAL METAL CONCENTRATIONS (Vg/g) IN CONTROL AND SLUDGE TREATED LOAM SOIL TAKEN FROM LYSIMETERS Metal Cd Depth (cm) Surface 1-5 5-10 Surface 1 - 5 5-10 Surface 1-5 5-10 Surface 1-5 5-10 Surface 1-5 5-10 Surface 1-5 5-10

No treatment 0. 6 < 0.4 0. 8 146 99 99 26 21 23 13 12 12 50 23 22 59 48 56

NPK ferti U s e r < 0.4 < 0.4 < 0.4 117 95 91 22 21 21 8 12 14 40 21 20 60 48 40

Al-sludge 15. 5 0. 5 < 0.4 1 190 108 94 630 37 27 32 15 8 380 37 17 350 55 48

Fe-sludge 5.5 < 0.4 < 0.4 517 110 84 210 42 24 15 12 18 255 87 24 135 50 49

Ca-sludge < 0.5 < 0.5 < 0.5 550 92 58 131 23 21 43 20 17 127 19 20 190 50 40

Zn

Cu

Ni

Pb

Cr

REFERENCES Black, S.A., 1980. Experience with phosphorus removal at existing Ontario In: R.C. Loehr, Phosphorus Management Strategies for

municipal wastewater treatment plants, pp 329-353. C.S. Martin and W. Rast (Eds.) Lakes. Ann Arbor Michigan 48106. Schmidtke, N.W., 1980. and W. Rast (Eds.) 48106. Slater, R.W. and Bangay, G.E., 1980. in the Great Lakes, pp. 13-25. W. Rast (Eds.) 48106. Thomas, N.A., Robertson, A. and Sonzogni, W.C., 1980. R.C. Loehr, C.S. Martin and W. Rast (Eds.) Strategies for Lakes. Ann Arbor, Michigan 48106. Webber, M.D., Soon, Y.K. and Bates, T.E., 1980. on land application of wastewater sludges. 905-917.

Science Publishers Inc., P.O.Box 1425, Ann Arbor, Sludge generation, handling and disposal at Phosphorus Management Strategies for Lakes.

phosphorus control facilities, pp. 361-390. In: R.C. Loehr, C.S. Martin, Ann Arbor Science Publishers Inc., P.O.Box 1425, Ann Arbor, Michigan, Action taken to control phosphorus In: R.C. Loehr, C.S. Martin and Ann

Phosphorus Management Stragegies for Lakes.

Arbor Science Publishers Inc., P.O.Box 1425, Ann Arbor, Michigan Review of control In:

objectives: New target loads and input objectives, pp. 61-90.

Phosphorus Management

Ann Arbor Science Publishers Inc., P.O.Box 1425, Lysimeter and field studies Prog. Water Tech. 12,

19-

PATHWAYS OF PHOSPHORUS IN SOIL R.E. White Department of Agricultural Science, University of Oxford, Parks Road, Oxford, 0X1 3PF, UK.
ABSTRACT Most of the P added to soil is taken up by the microbial by the increased of fresh residues supply between mineralisation of the substrate growth yield to the equation: P/C substrate Solving the critical mineralising assess ratio desorption are this = p (1 - CF) -- + CF C ' C/P r mm using data from the literature The equation solution can also is buffered suggests be used by the that were to from which micro-organisms in plant residues and animal The the excreta stimulated balance ratio their according decomposition feeding, (C/P )

biomass,

the growth of which is carbon substrates. of P during will their matter within

of energy-rich and immobilisation organic

or humified

depend on the C/P tissues

on which the micro-organisms

are actually

(CF) and the C/P ratio

equation

C/P ratio

of the substrate 50 and 70.

P lay between of P at solid decomposed. of soil because

the extent

to which P in the soil surfaces

when simple matter Further studies

substrates

of known C/P variable the to of under

The C/P ratio than the C/N ratio stabilised chemical prove less microbial specified agricultural nature in organic rewarding biomass conditions.

organic

is known to be more efforts of soil to determine organic

of the variety

of ways in which P may be P are likely of change better of P in

combination. than kinetic

of the unknown components P, metabolite

in which the rate inorganic should biomass emerge a

P and labile

P are measured

From such experiments of the microbial ecosystems.

understanding

of the role and natural

in the cycling

-21-

DEFINING THE PROBLEM The pathway of phosphorus (P) is perilous - for of the P which is diverted from tight circulation within the soilplant-animal system almost all ends up in waste, as illustrated in Figure 1. The main input to the soil-plant-animal system (SPAS) is water soluble P fertiliser made from rock P which is mined from sedimentary deposits laid down in the distant past. Some P is lost from the SPAS by erosion of P-enriched surface soil, and to a much smaller extent by leaching (usually < 1 kg P/ha/year. But the bulk of the P removed from the SPAS, in plant and animal products, eventually goes to waste treatment plants from which it emerges in the sludge (which contains more P in inorganic (P.) than organic forms (P ) and liquid effluent (which has roughly equal proportions of P. and P ) . Some sludge (and the bulk of animal slurries) is spread on agricultural land, but most of the P in waste materials passes into rivers, lakes and the sea, and especially into submarine sediments where it is immobilised as insoluble calcium phosphates of variable composition. Despite the waste of P as described, the regular application of fertiliser P to agricultural land has resulted in a steady increase in P residues in the soils (Larsen,19 73), especially in the developed countries of Europe and North America. With recent rapid rises in the cost of rock P, the political instability of many of the producing countries and concern over environmental pollution (eutrophication of surface waters), it is pertinent for agricultural scientists to seek to improve the utilisation of the large reserves of P in agricultural soils, and to this end, increasing attention has been focussed during the last 10 years on the cycling of P in soils (Halm et al., 1972; Cole et al., 1977).

22-

Prec pitation

Return to land

SOIL - PLANT ROCK P - ANIMAL SYSTEM

PRODUCTS

WASTE TREATMENT

Erosion

Drainage

Effluent
*

p r n n r i l T P

^ FRESHWATER
SEAWATER

SEDIMENTS ^
Pj +++

SLUDGE Po +
Pi + +

f Pi lPo +

Fig.l: The global P cycle

Elaborate flow-diagrams for P cycling have been proposed (e.g. Figure 2) in which an itinerant P atom might be excused for being confused about the pathway it was expected to follow. To simplify my presentation, in the hope of avoiding similar confusion in the minds of my audience, I have redrawn the P cycle (Figure 3) to highlight those parts of the cycle about which I wish to speak - that is, the transformation of P in organic residues via the microbial biomass into the relatively stable soil organic pool (P ) and the pool of labile P from which plants draw their supply. Quantities of P in each compartment are given in parentheses and the arrowheads indicate the position of equilibrium of each reaction when a steady-state is achieved. DECOMPOSITION OF ORGANIC RESIDUES ADDED TO SOIL The bulk of the P in plant residues or faeces deposited on the soil is incorporated into the soil microbial biomass, the growth of which is stimulated by the increased supply of energy-rich C substrates (Birch,1961; Enwezor,1966; Floate,19 70; Chauhan et al.,19 79). Exceptionally, some inorganic P may be leached directly into the soil when heavy rain falls on mature ('hayed-off') grasses and legumes (Bromfield and Jones,1972); also some plant phytin (the Ca and Mg salts of the phosphate esters of inositol) may contribute directly to the P fraction but this is unlikely to exceed 3% of the soil organic P (Cosgrove,19 7 7). The incorporation of P into microbial tissues is called immobilisation; its subsequent release - the process of mineralisation - depends on the rate of growth and decay of the microbial population and on the decomposability of the microbial metabolites that are formed. Data obtained in our laboratory at Oxford by A.T. Ayoub for the incubation of dried Viaia faba tops in moist sand illustrate the changes with time in mineral P (extracted in 0.5 M NaHCO., at pH 8.5), biomass P (determined by the chloroform fumigation technique of Jenkinson

-24-

PHOSPHORUS

CYCLE

0-10

Fig.2: P cycling in semi-arid grassland (after Chauhan et al.,1979) Values in g P m -25-

Labile

(soln + adsorbed) (1-100)

Microbial biomass (8-20)

Plant residues, animal excreta (5-30)

Resistant org. P compounds Non-labile P (chemisorbed P and insoluble P compounds)

Animals

(100- 500)

Plants (10-40)

(200-1000 )
Fig.3: A simplified P cycle in soil (all figures kg ha 15cm)

1g

dried C/P

Vicia ratio

faba 251

to

100g

sand

(0-167/. P )

25C

E o. A c
6>

Metabolite P

c o o

Fig.4: Changes in soluble P, biomass P and metabolite P during the decomposition of Vieia faba in sand

-27-

and Powlson,19 76) and microbial metabolite P (determined as the residual P not ext: extractable in 0.5 M NaHCO, after CHC1 3 fumigation) (Figure 4) THE INFLUENCE OF C/P RATIO The conventional approach to predicting whether net mineralisation or immobilisation of P occurs when organic matter decomposes rests upon identifying a critical ratio of C to P in the substrate used by the micro-organisms, in a manner analogous to assessing a critical C/N ratio above which N immobilisation occurs and below which there is mineralisation. A review of recent literature reveals a wide range of critical C/P ratios, as shown in Table 1.
TABLE 1 RANGE OF CRITICAL C/P RATIOS 55 < 303 > 63 > 77 133 > 183 200 > 286 > 300

Barrow, 1960 Floate, 1970 Dalai, 1979 Kaila, 1949 Singh and Jones, 19 76 (Black and Goring, 1976 (Alexander, 1977 Chauhan et al., 1979 Blair and Boland, 1978

Fenchel and Blackburn (19 79) point out that the critical C/P ratio of the substrate is determined by the C/P ratio of the microbial biomass formed (Cm/Pm ) and the efficiency 1 with which the microbes convert C into cell substance, i.e. the growth yield or CF value. The critical C/P ratio is then calculated as (Cm/Pm )/growth 3 - 1 yield, as shown in Table 2. A wide range of values for C /P and growth yield has been reported, depending on the type of organisms studied and whether decomposition is aerobic or anaerobic (Table 3 ) . An average value for the growth yield of soil micro-organisms growing aerobically is 0.5
-28-

(Jenkinson, 1976) but this may fall as low as 0.05 under anaerobic conditions (Paul and van Veen, 1978; Fenchel and Blackburn, 1979). Bacteria usually have a lower C /P J m m ratio than fungi and a value between 20 and 50 seems appropriate for mixed populations, although Ayoub's work in our laboratory suggests the C/ P ratio may approach 100 in micro-organisms feeding on substrate of C/P ratio = 500. The low C /P ' m' m ratios ( = 20) for bacteria may reflect their ability to take up excess soluble P and store it as linear polyphosphates (volutin granules), as suggested by Pepper et al. (1976).

TABLE 2 MICROBIAL METABOLISM OF SUBSTRATE CARBON

(C assimilated) Then microbes have a growth yield = and a C /P

For the substrate to supply microbial demand for P, its C /P ratio must be C m C
v <

a m

m m

* - F"

F"

i.e. Critical C/P ratio :

C/P ratio of microbes G r o w t h yield

29-

TABLE 3a ESTIMATES OF MICROBIAL GROWTH YIELD

AEROBIC CONDITIONS Fungi Bacteria 0.3 - 0.4 0.05 - 0.1 Alexander, 19 77

Actinomycetes 0.15 - 0.3 Soil organisms 0.4 - 0.6 Soil organisms 0.5 ANAEROBIC CONDITIONS Bacteria 0.05 - 0. 3 0.025 Fenchel and Blackburn, 1979 Paul and van Veen, 1978 Paul and van Veen, 1978 Jenkinson, 1976

TABLE 3b ESTIMATES OF MICROBIAL C/P RATIOS

Fungi Bacteria Bacteria Microbial biomass

n
ii

50 - 100 Alexander, 1977 17 - 50 20 20 - 35 50 - 100 45 - 92 Fenchel and Blackburn, 1979 Chauhan et al., 1979 Cole et al., 1977 Ayoub, 1980

-30-

0-2

0-3

04

05 yield of

0-6

07

0-8

Growth

biomass

Fig.5: Response surface relating critical C/P ratio to growth yield and C/P ratio of microbial biomass

- 31

The effect of varying C /P ratio and growth yield (CF m m value) of micro-organisms on the critical C/P ratio for mineralisation vs. immobilisation can be expressed by a response surface, as illustrated in Figure 5. For a C /P ratio of 50 m m and a CF value of 0.5, the critical C/P ratio of the substrate is 100. Alexander(19 77) opts for a critical C/P ratio of 200, suggesting that "during the early stages of decomposition,when the C/P ratio is >200, immobilisation occurs but once the C/P ratio drops below 200, mineralisation occurs". One expects the critical C/P ratio to depend on the stage of decomposition because as decomposition proceeds and one generation of microorganisms is succeeded by another, which feeds on the tissues of the first, the growth yield of the population will decline (Paul and van Veen, 19 78) so that the critical C/P ratio of the substrate appears to rise. One therefore moves upwards and to the left across the response surface in Figure 5 (for a C n/ P m = 5 0 a n d a g r o w t h yield of 0.5 x 0.5 = 0.25, the critical C/P ratio = 200). Other factors which in the short term may influence the balance between mineralisation and immobilisation are the ease of decomposability of the C compounds and the proportion of orthophosphate and readily hydrolysable sugar phosphates in the original residues. Apart from studies on single substrates (e.g. glucose and cellulose being the most popular) there is relatively little empirical evidence to indicate what fraction of the C compounds of natural residues is most easily decomposed. Carbon soluble in hot or cold water has been measured (Dalai,1979; Ayoub,19 80) and this is quite variable (Table 4 ) , as is the proportion of soluble or bicarbonate extractable P to total plant or faecal P (Table 5 ) . Thus, the critical C/P ratio is expected to vary with the type of material being decomposed (fresh plant residues,faeces or resistant soil organic matter), its proportion or P. , the dominant type of micro-organism and the period of decomposition.

-32-

TABLE 4 RANGE OF WATER-SOLUBLE CARBON IN PLANT MATERIALS Wat_er_-soiubl C ( % dry matter) Tri folium Dalai,1979 shoots roots Viaia faba shoots extracted in hot water for 2 hr. Ayoub,1980 25.5 42.0 3.5 1.9 38.1 34.9 repens ^P^al^ C

extracted in cold water for 1 hr.

TABLE 5 P. AS A PROPORTION OF TOTAL P IN PLANT RESIDUES AND ANIMAL FAECES

1

( % ) F e s t u c a , Agrostis,Nardus Sheep faeces Floate,1970 Floate,1970 58 - 66 76 - 81 47 - 87

60 - 85 33 - 78 68 71 72 81

Tropical grasses,young to mature Birch,1961 Grasses and subterranean clover Sheep faeces Viaia faba shoots - freeze-dried - dried at 50C for 2 days - dried at 70C for 2 days Bromfield and Jones,1972 Bromfield and Jones,1970 Ayoub,1980

-33-

An alternative approach to the problem of predicting the C/P ratio is to determine the actual C/P ratio of the substrate on which micro-organisms known to be mineralising P are feeding. To do this, one must expand the Fenchel and Blackburn equation, Critical C/P ratio C /P
m m

CF

to include a term for the amount of C and P mineralised in a given time, on the assumption that the C of the substrate goes either to C02(C ) or into microbial cell structure and intracellular metabolites (C), and the P goes either to mineral P = m in the medium (P ) or into cellular substance and metabolites m i . e . S u b s t r a t e P/C = S i n c e C r + Cm = ^ - ^ P_ + P_ r
+

(1) (2)

md

VCr = r ^ c f
(1 - CF) r P P (1 - CF) g + (1 - CF) ^ r r P P C (1 - CF) g + (1 - CF) J 5 ^ r m r gives
c

(3)

(P_ + Pm) P/C substrate = ^ =

(4) (5)

= S u b s t i t u t i n g f o r C /C

(6)

from (3) and s i m p l i f y i n g P P/C s u b s t r a t e = (1 - CF) -^- + ^ - / p r ^m7^

(7)

Substitution of measured values of C , P , CF and C /P r r m m in equation (7) enables one to calculate the P/C ratio of the substrate actually metabolised. (Note that when P = 0, CF equation (7) reduces to P/C = =7=r C /P C_/P / _ m m m' m or C/P = C F
-34-

which is identical to the Fenchel and Blackburn equation in Table 2. One may test the validity of equation (7) using data for the decomposition of fresh plant residues and soil organic matter for which P mineralisation has been observed. For example, Thompson et al. (19 54) reported the P /C ratio for cultivated and virgin Iowa soils was 1 : 114 and 1 : 80 respectively. Taking CF = 0.5 and C /P = 5 0 and substituting m m in equation (7) we have: Substrate C/P ratio for cultivated soils = 69 and for virgin soils = 62. D a l a i (19 79) f o l l o w e d t h e m i n e r a l i s a t i o n of 14 C and white c l o v e r r o o t s and s h o o t s i n a Yellow P o d z o l i c s o i l f o r 10 w e e k s . One can c a l c u l a t e from h i s d a t a t h a t t h e r a t i o of P /C for r o o t and s h o o t d e c o m p o s i t i o n was 0 . 0 2 0 3 and 0.009 7 r e s p e c t i v e l y ; h e n c e , u s i n g t h e ' s t a n d a r d ' v a l u e s f o r CF and C /P m t h e s u b s t r a t e C/P r a t i o was e q u a l t o 50 and 68 f o r r o o t s and s h o o t s respectively (this i s consistent with the higher proportion of c o l d - w a t e r s o l u b l e C i n t h e s h o o t s ) . F i n a l l y , Ayoub (1980) measured C and P m i n e r a l i s a t i o n when Viaia faba s h o o t s of v a r y i n g P c o n t e n t were decomposed i n s a n d f o r 30 d a y s ; i n d e p e n d e n t e s t i m a t e s of CF (=20) and = C/P results m m r a t i o (=50) were made. One o b t a i n s t h e f o l l o w i n g on s u b s t i t u t i o n i n e q u a t i o n ( 7 ) : Decomposition of Vieia faba shoots in sand I n i t i a l C/P ratio of plant material
506 251 123 Calculated C/P ratio of microbial substrate after 10 days 196 108 64 + Net mineralisation (+) or immobilisation ( ) of P after 30 days 32 T 'P l a b e l l e d compounds d u r i n g t h e d e c o m p o s i t i o n of

35-

It appears that, irrespective of the period of decomposition, when fresh plant residues or humified soil organic matter decompose with a net release of P., the C/P ratio of the substrate utilised by the micro-organisms lies between 50 and 70. More data are needed to confirm this conclusion, but it is certainly consistent with Barrow's (1960) observation that the critical C/P ratio for mineralisation was 55 when micro-organisms were grown on a substrate containing P in an organic form only (as sodium S-glycerophosphate) . Prediction of P mineralisation and the buffering of Pj in the soil solution. Equation (7) can also be used to predict the change in P. in the soil solution when simple substrates (glucose, cellulose) are decomposed. The calculated value of P_(+) m ay be compared with the measured change in soluble P. (by NaHCO.. extraction), to assess the extent to which the solution P has been buffered by adsorption or desorption of P. The experiments of Chauhan et al. (19 79) serve to illustrate: during the first 30 days of incubation of cellulose and NH.NO, with a Chernozemic Black soil (soluble P.= 15 ppm) the predicted fall in soluble P. was 2.4 ppm compared with a measured fall of 5 ppm. After 9 months of incubation with monthly additions of cellulose plus N, the predicted fall in P. was 21.6 ppm, compared with an actual fall of 6.5 ppm. Therefore, some 15 ppm was supplied from the labile pool not initially extractable in 0.5 M NaHCO.,. This P may have been drawn from the resin-extractable pool wnich fell from 45.1 to 28 ppm (a drop of 17 ppm) over this period. On the other hand, soils low in soluble P. (due to their high affinity for P) are likely to exhibit reduced recoveries of P even when materials of low C/P ratio are decomposed. Ayoub (1980) found that 40 days after the addition of glucose and KHP0. to a black clay soil of the Gezira to give an initial C/P ratio of 58, the predicted value of P r from equation (7) was 5 2 ppm whereas the actual value of soluble P. was 5 ppm. Clearly, most of the P mineralised (some 47 ppm)
-36-

had been readsorbed by the soil in a form not extractable in 0.5 M NaHCO... Indeed, in a control soil to which the same amount of P but no glucose was added, the soluble P. after 40 days was 9 ppm, indicating that 59.4 ppm out of the original 68.4 ppm of NaHCO, extractable P. in this soil was immobilised by the physico-chemical processes of adsorption and precipitation alone in 40 days. SOIL ORGANIC PHOSPHORUS Primarily as a result of microbial activity, and to a lesser extent the accretion of resistant plant organic phosphates, organic P may accumulate to as much as 85% of the total soil P. The topic of soil organic P has been extensively reviewed (Halstead and McKercher, 1975; Cosgrove, 1977; Dalai, 19 77): I shall therefore say little other than to point out that whereas C and N are intimately associated in humified organic matter, P may be stabilised independently of the process of C transformation, so that the C/P ratio of soil organic matter tends to be much more variable than the C/N ratio (Dalai,1977). Williams and Steinbergs (1958) suggested that soil organic P can be subdivided into a part that is intimately bound to C,N and S and another variable proportion that comprises independent P compounds, mainly P esters. The latter have been identified as predominantly the penta- and hexaphosphate esters of myo-inositol (iP5 and iP6) which can comprise up to 60% of the organic P (Cosgrove, 19 77). Small amounts (3 - 10%) of nucleic acids and their derivatives and phospholipids (^1%) are also found, but the chemical nature of the remainder, amounting to 40 - 90% of the total organic P, is obscure. The average C/P ratio of a 1 : 1 mixture of iP5 and iP6 is 0.42 so there is apparently little microbial breakdown of these compounds in soils actively mineralising P, for which the critical C/P ratio of the substrate has already been shown to lie between 50 and 70. Indeed, the stability of these

-37-

compounds especially under acid conditions has been attributed to their strong adsorption by clay minerals (Anderson et al.,19 74) However, hydrolysis of one or two of the ester groups of iP5 or iP6 by phosphatase enzymes produced by plant roots or soil micro-organisms could account for P mineralisation that was not directly linked to the metabolism of the whole inositol molecule. There is another possible cause of variability in the C/P ratio of soil organic matter. Sorption of P. by soils is frequently correlated with soil organic matter content (Williams et al., 1958; Harter, 1968), and especially with the amount of Al and Fe associated with the organic matter. Work in our laboratory with peat, humic acid extracts and weak anion-exchange resins has shown that although the amount of P adsorbed per gram is broadly correlated with the amount of Al on the organic exchanger, it also depends on the degree of hydrolysis of the Al. Our results and those of Appelt et al. (1975) show that as the average charge per adsorbed Al atom decreases, the mole ratio of adsorbed P to adsorbed Al decreases (Figure 6 ) . Thus, the amount of P adsorbed per gram of organic material can vary quite widely for a given Al (or Fe) content (Figure 7 ) . The C/P ratio in these hydroxy Al-organic matter complexes containing adsorbed P, as calculated from the data of Figure 7 assuming a C content of 40%, ranged from 92 to 1173. It is therefore possible for the C/P ratio of the constituents of soil organic matter to range from >1000 to <1. Depending on the proportions thesei constituents make of the whole, the C/P ratio of organic matter would also vary widely, as reported above. These observations also support the view of MacGill and others (unpublished) that the mechanisms controlling the mineralisation of C and P in soil organic matter are not necessarily the same - C is required for energy and cell growth; some P is released concomitantly with C mineralisation, but P is also released through the action of extra-cellular phophatases and due to the desorption of P ionically bonded to metal ions associated with negatively
-38-

0-6r

05-

Data from Appelt et al. (1975)

Data

for

peat, humic acid and resin

1 Average

+2 charge per Al atom

*3

Fig.6: Variation in P/Al mole ratio of adsorbed material on organic exchangers.

39-

60 P sorbed (pmol g~1) 50-

o,

Peat samples Humic acid fraction Resin samples

A0-

30"

20-

10"

100

200

300

400

500

600

700

-^

2200

2300

Al content of exchanger (>imol g" )

Fig.7: Relationship between P sorbed by organic exchangers and their Al content (after White and Thomas,1978).

charged organic compounds. Thus, further efforts to elucidate the chemical nature of the unknown fraction of soil organic P may not be rewarding but more studies of the kinetics of P transformation through the biomass should throw light on the contribution that microbial P makes to the build up of organic P and to labile P in soil.

-41-

REFERENCES

Alexander, M. 1977.

Introduction to soil microbiology, 2nd. Ed.

Wiley, New York. Anderson, G., Williams, E.G., and Moir, J.O. 1974. A comparison of the sorption of inorganic orthophosphate and inositol hexaphosphate by six acid soils. J. Soil Sci. 25, 42-51. Appelt, H., Coleman, N.T., and Pratt, P.F. 1975. soils II. Ayoub, A.T. 1980. Interactions between organic compounds, minerals, and ions in volcanic-ash-derived Effects of organic compounds on the adsorption of The effect of phosphorus transformations on soil phosphate. Soil Sci. Soc. Am. Proc. 39_, 628-30. phosphate availability during the decomposition of green manure. D. Phil, thesis. University of Oxford. Barrow, N.J. 1960. The effects of varying the nitrogen, sulphur and phosphorus content of organic matter on its decomposition. Aust. J. agric. Res. ]a, 317-330. Birch, H.F. 1961. Phosphorus transformations during plant decomposition. Organic phosphorus in soils. In: PI. Soil. 15, 347-366 Black, C.A. and Goring, C.A.I. 1953. Soil and fertilizer phosphorus in crop nutrition (Eds. W.H.Pierre and A.G.Norman), Agronomy No. 4_, 123-152 Blair, G.J. and Boland, O.W. 1978. The release of phosphorus from plant The effect of sheep on the material added to soil. Aust. J. Soil Res. 16, 101-111. Bromfield, S.M. and Jones, O.L. 1970. Res. 21^, 699-711. Bromfield, S.M. and Jones, O.L. 1972. agric. Res. 23_, 811-824. Chauhan, B.S., Stewart, J.W.B. and Paul, E.A. 1979. phosphate. Can. J. Soil Sci. 59_, 387-396. Cole, C.V., Innis, G.S. and Stewart, J.W.B. 1977. Cosgrove, D.J. 1977. Simulation of phosphorus cycling in semi-arid grasslands. Ecology 58, 1-15. Microbial transformations in the phosphorus cycle. Adv. Microbiol. Ecology 1, 95-134. Effect of carbon additions on soil labile inorganic, organic, and microbially held The initial leaching of hayed-off pasture plants in relation to the recycling of phosphorus. Aust. J. recycling of phosphorus in hayed-off pastures. Aust. J. agric.

-42-

Dalai, R. C.1979.

Mineralization of carbon and phosphorus from carbon-14

and phosphorus-32 labelled plant material added to soil. Soil Sci. Soc. Am. J. 43_, 913-916. Dalai, R.C. 1977. Soil organic phosphorus. Advances in Agron. 29, 83-117. The biological transformation of phosphorus during Enwezor, W.O. 1966.

the incubation of a soil treated with soluble inorganic phosphorus and with fresh and rotted organic materials. Pi. Soil. 25, 463-466. Fenchel, T. and Blackburn, T.H. 1979. Academic Press, London. Floate, M.J.S. 1970. Mineralization of nitrogen and phosphorus from organic materials of plant and animal origin and its significance in the nutrient cycle of grazed upland and hill soils. J. Br. Grassland Soc. 25_, 295-302. Halm, B.J., Stewart, J.W.B. and Halstead, R.L. 1972. in a native grassland ecosystem. Halstead, R.L. and McKercher, R.B. 1975. phosphorus. 4_, 31-63. Harter, R.D. 1969. Phosphorus adsorption sites in soils. Soil Sci. Soc. The effects of biocidal treatments Am. Proc. 21/ 6 30-2. Jenkinson, D.S. and Powlson, D.S. 1976. Soil Biol. Biochem. 8 _ , 209-213. Jenkinson, D.S. soil IV. Kaila, A. 1949. Larsen. S. 1973. 1976. The effect of biocidal treatments on metabolism in The decomposition of fumigated organisms in soil. Biological absorption of phosphorus. Soil Sci. 68_, 279-289. Recycling of phosphorus in relation to long term soil on metabolism in soil V. A method for measuring soil biomass. The phosphorus cycle In: Isotopes and Radiation in Biochemistry and cycling of Bacteria and mineral cycling.

Soil-plant relationships incl. Forestry. IAEA. Vienna 571-585. In: Soil Biochemistry (Eds. E.A. Paul and A.D. McLaren)

Soil. Biol. Biochem. 8_, 203-208.

reserves. Phosphorus in Agriculture No. 61, 1-6. Paul. E.A. and van Veen, J.A. 1978. The use of tracers to determine the dynamic nature of organic matter. Trans. 11th intern. Congr. Soil Sci. Vol. 3, Edmonton, Canada. Pepper, I.L., Miller, R.H. and Ghoniskar, C.P. 1976. Soil Sci. Soc. Am. J. 40, 872-875 Microbial inorganic polyphosphates; factors influencing their accumulation in soil.

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Singh, B.B. and Jones, J.P. 1976. Soc. Am. Proc. 40, 389-394.

Phosphorus sorption and desorption

characteristics of soil as affected by organic residues. Soil Sci. Thompson, L.M., Black, C.A., and Zoellner, J.A. 1954. Occurrence and

mineralization of organic phosphorus in soils with particular reference to associations with nitrogen, carbon and pH. Soil Sci. 77_, 185-196. White, R.E. and Thomas, G.W. 1978. Edmonton, Canada. Williams, C.H. and Steinbergs, A. 1958. Sulphur and phosphorus in some Soil properties and eastern Australian soils. Aust. J. agric. Res. 9 _ , 483-491. Williams, E.G., Scott, N.M. and McDonald,M.J. 1958. phosphate sorption. J. Sci. Food Agric. 9, 551-559. Phosphate retention by Al-charged organic exchangers. Trans. 11th. intern. Congr. Soil Sci. Vol.1

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DISCUSSION
R. Gerritse (Netherlands)

I would like to contend that in order to elucidate the phosphorus cycle in the soil, more attention should be paid to the nature of the phosphorus compounds in the soil solution, because all the reactions through micro-organisms will take place mainly by way of the soil phosphorus compounds. So, you should not look at the bulk phosphorus compounds in the soil but rather at the phosphorus compounds in the soil solution. I know from my own experiments that a large part of the phosphorus in the soil solution is contained in organic phosphorus compounds of fairly high molecular weight. I believe that concentrating more on this aspect in the future will throw more light on the actual phosphorus cycle in the soil. What is your opinion on this? R.E. White (UK) We have been interested in the organic phosphorus compounds in solution. However, working in most agricultural soils it is very difficult to get enough of these materials out of the soil solution to identify them unequivocally. The other point I would make is that I know of no evidence, although I would be grateful to hear of any, that there is considerable buffering of this concentration of organic phosphorus in the soil solution other than through the microbial uptake for decomposition. With inorganic phosphorus we know that there is a very strong buffering mechanism which operates between the solid surfaces, where the bulk of the inorganic phosphorus is, and the solution. However, although we can extract organic phosphorus in solution, we do not know how well that is replenished when a plant takes up phosphorus from solution, or when a micro-organism takes it up, other than through this rather slower microbial decomposition or uptake process. A. Cottenie (Belgium) It is possible to determine phosphorus in the soil by at
-45-

least fifty different methods. Would you recommend one particular method here for determining the phosphate content in order to calculate the same C : P ratio? R.E. White Well, I know that a lot of phosphate chemistry is bedevilled by analytical problems and that of determining organic phosphorus in soil is probably the worst one of them all. In our experiments we did not measure organic phosphorus in the soil because we thought it would be a profitless exercise. The point I was trying to make was that I think we can get at the C : P ratio of the microbial substrate by indirect means rather than having to worry about total analysis of the soil for organic phosphorus, or any part of the total phosphorus of the soil. I think we are fairly sure of our analytical methods for analysing phosphorus in solution; we are not sure about the partitioning of phosphorus between organic and inorganic phosphorus on a total basis.

46-

LONG TERM PHOSPHATE BINDING CAPACITY OF SOME SOILS* W.H. van Riemsdijk and F.A.M. de Haan Department of Soils and Fertilisers, Agricultural State University, De Dreyen 3, 6703 BC Wageningen, The Netherlands. ABSTRACT Phosphate at constant technique, constant super-saturation sorption experiments primarily The reaction to dS/dt of metal are described to metal with an acid sandy phosphates. (c rate This at with oxides accompanying to the to -stat) soil constant

super-saturation was obtained which enables

with respect accurate

by the phosphato-stat of the reaction rate

measurement

super-saturation. St according of coatings

is found to decrease on top of the metal on the is also applicable of the

amount sorbed, the formation present cation systems implying capacity

= k~ exp (-kpS). phosphates rate rate

This is ascribed

in the soil. (Na, K). that that it already

The reaction contain

is also dependent equation at the start

The above mentioned phosphate can be used for agricultural

measurements, sorption

the prediction soils.

of the long term

of similar

* Part of this text will also be published in the Journal of the International Soil Science Society of America.

-47-

INTRODUCTION The kinetics of the phosphate sorption reaction with soil are of prime importance if one wants to construct a mathematical model describing the movement of phosphate through soil at a given application rate (Mansell et al., 1977; Enfield, 1977; Novak and Petschauer, 1979; Beek, 1979). Understanding of the sorption reaction mechanisms and its kinetics are thus a prerequisite if one wants to predict the amount of phosphate that can be applied to the soil without risk to the environment. The same information may also be of use in helping to develop more efficient phosphate fertilisation procedures. The phosphate sorption may consist of adsorption and/or precipitation like reactions. Due to the low solubility of several phosphate containing minerals, precipitation may already occur at very low phosphate concentration. However, in general it is very difficult to unravel the total sorption into its different contributions. Generally one thus distinguishes fast and slow processes. Many authors (Novak, 197 6; Overman and Chu, 1977a, 1977b; Enfield et al., 1977; Novak and Petschauer, 1979) consider the slow reaction to be a first order reaction, either with respect to phosphate concentration (c ) or with respect to adsorbed phosphate. A detailed study on the reaction of phosphate with gibbsite (Van Riemsdijk and Lyklema, 1980a; 1980b) however, comes to quite different conclusions. The main features of the sorption kinetics in these studies were found as: a) Initially adsorption is the dominant reaction mechanism, with an adsorption maximum that is determined by the amount of singly co-ordinated 0H(H) groups present on the hydroxide surface; the adsorption maximum is already approached at c values as low as 20 ymol/1. At high degree of super-saturation surface precipitation is the dominant reaction mechanism, almost from the start of the experiment.
-48-

b)

c)

The rate of precipitation increases with increasing super-saturation and decreases with the amount reacted.

d)

The cation in the system (K , Na , etc.) influences the kinetics.

The research described here was undertaken to test whether the phenomena observed in the Al (OH) ..-phosphate system would also occur in soil. The soil used contains a very low fraction of organic matter, some feldspars and iron and aluminium oxides-hydroxides, no calcium carbonate, and a negligible clay fraction. The reaction of phosphate will thus be restricted to sorption (adsorption and/or precipitation) on feldspars and aluminium and iron oxides-hydroxides. The oxides may be present as individual particles or as coatings on quartz particles. The oxides will most probably contain some organic matter that will influence their structure and thus the sorption characteristics (Ng Kee Kwong and Huang, 197 8 ) . If first order kinetics apply for the slow part of the sorption, the reaction rate of a system with constant and high super-saturation should become constant after a relatively short time (see a - b above). order with respect to c This holds equally for first as with respect to amount adsorbed, For these reasons over a consider-

the latter because adsorbed phosphate also has to become constant after some time in such a system. all experiments were performed at a constant c

able range of total sorption, S (mmol/kg), in order to discriminate clearly between first order kinetics and kinetics where the amount sorbed decreases the reaction rate. It may be noted that the equilibrium situation for the experiments reported here would be a complete conversion of the aluminium and iron oxides, and feldspars to corresponding metal phosphates. sorption maximum. This then corresponds with the theoretical Rate equations that predict equilibrium are thus not in

sorptions (dS/dt = 0) that are a function of c

-49-

agreement with the fundamentals of the precipitation process. This, however does not necessarily mean that such a type of equation cannot mathematically describe the sorption data over a restricted range of S and t. A decrease in precipitation rate during the course of an experiment at constant super-saturation may for instance be caused by: I) II) III) the presence of different sorbents with different reactivities; a decrease of reactive surface area during sorption; the formation of a surface layer of increasing thickness through which diffusion has to take place to let the reaction proceed.

MATERIAL AND METHODS The soil used was a sandy soil, according to the Dutch Soil Classification a 'Kanteerd' Soil (De Bakker and Schelling, 1966), and has not been in use for agricultural purposes. Samples were taken at a depth of 70 - 80 cm. The extractable iron and aluminium of the soil samples was determined by three successive extractions with citrate-dithionite-bicarbonate (CDB) (Mehra and Jackson, 1960) and with acid ammonium oxalate (OX) (Tamm, 1934; Schwertmann, 1964). Table 1 presents some data of the samples used in the experiments. The phosphato-stat is based on the experimental fact that the ratio of the OH production and phosphate sorption becomes constant after a relatively short reaction time (minutes) for a super-saturated system. The heart of the experimental set-up is in fact a pHstat system that is made to function as a phosphato-stat as well by using an acidified phosphate solution in the burette (of the pH-stat) instead of the ordinary titrant (HC1 or NaOH). The proper composition of the burette solution for the phosphatostat can be calculated if the experimental parameters are known, such as pH and c of the reaction system and the OH/P ratio

mentioned above. For more details see Van Riemsdijk and Lyklema (19 80a, 19 80b).
TABLE 1 SOME DATA OF THE SOIL SAMPLES USED IN THE EXPERIMENTS

Al

Fe

Al

Fe

Al

Fe

Organic C

mmol/kg

mniol/kg

mmol/kg

(total)

(CDB)

(OX)

464

104

71

33

65

0.23

The conditions of the experiments were: 300 ml 20 mmol/1 NaCl or KC1; 90 gram soil; pH = 4.62 (= equilibrium pH of the soil in this solution); different c values in the range of P 0.1 mmol/1 to 10 mmol/1 (NaH-PO. or KH 2 P0.). The soil was put in the reaction vessel together with the background electrolyte, stirred for 1 to 1.5 h and kept at pH 4.62 with HC1 and/or NaOH. After this time the drift in pH was negligible. Then phosphate was added to the system and the pH was kept constant with the phosphato-stat set up. At time intervals samples were taken and analysed for phosphate after filtration. The stirring of the reaction system may cause some decomposition of the soil particles (Beek, 1979; Barrow and Shaw, 1978) , thus possibly increasing the surface area of the soil during the experiment. This effect, if present at all, will probably be the largest in the pre-equilibration period (before the phosphate is added). If it still occurs during the phosphate sorption its effect will be an increase of the reaction rate with time. As will be shown this effect is not strong enough to obscure the precipitation mechanism. The
51

experiments lasted 3 to 5 days. To be able to estimate the effect of the experimental conditions on the reaction rate with respect to prolonged reaction time and stirring, socalled batch experiments were also performed. These experiments are described in more detail in Van Riemsdijk (197 9). RESULTS AND DISCUSSION Phosphato-stat experiments Preliminary experiments indicated that the ratio between the hydroxyl production and phosphate sorption, R, was constant after some time. This constant ratio allows the construction of the so-called phosphato-stat (see Materials and Methods). The ratio varied somewhat for the different experiments (Figure 1). It seems that the ratio decreases slightly with increasing c value. According to the reasoning as presented in Van Riemsdijk and Lyklema (1970a, 1980b), this may indicate that the cosorption of cations is somewhat dependent on c . The c value decreased slightly during the experiments due to a difference in the pre-estimated R-value and the measured R-value. The deviation from the average concentration, c , was less than 6% except for experiment 1 where it was 19%. All the reported sorptions are calculated from the amount of phosphate added during the Experiment and from the measured change in c . The sorptions of the different experiments as a function of /t (t = time) are shown in Figure 2. It is to be expected (Van Riemsdijk and Lyklema, 19 80a, 19 80b) that precipitation phenomena already dominate the reaction kinetics shortly after the start of the experiments (minutes to a few hours) due to the high super-saturations involved. This is supported by the constancy of the R-value after a short reaction time (Van Riemsdijk and Lyklema, 1980a, 1980b). Broken lines, calculated from linear regression analysis for t > 1 h, are drawn also in Figure 2. The shape of the measured curves suggests that the precipitation is not
-52-

4!

V 2-

10 mmol/kg

12

Tig. 1.

The amount of acid required to keep the pH constant as a function of phosphate sorption for 5 phosphato-stat experiments; pH 4.62, 20 C. Experiments 1 to 4 had 20 mmol/1 NaCl as supporting electrolyte using NaH-PO. as the source of phosphate; Experiment 5 had 2o mmol/1 KC1 as supporting electrolyte and KH_P0. was used. Data of linear regression analysis are given below, s* indicating the intercept with the horizontal axis.

xp.

r^
0.999 1.000 0.998 0.993 0.999

r
0.707 0.708 0.661 0.628 0.529

s* (mmol/kg 1.67 2.93 8.86 7.69 6.67

1 2 3 5 6

-53-

7 e 9 10 Reaction lime (hr,/2l

Fig. 2.

Sorption of phosphate on sandy soil at (phosphato-stat) as a function of /t. are given in Figure 1. Data of linear lines) for t > 1 h according to S = k

constant c and pH The experimental conditions regression analysis (broken /t + k_ are given below.

Exp 1 2 3 4 5 0.964 0.958 0.961 0.995 0.969

1 0.291 0.580 0.768 0.995 0.937

54-

2 3.04 4.24 4.69 7.56 12.2

adequately described by this type of equation (S = k /t + k,) in spite of the close agreement between calculated and measured values. Experiments over longer reaction times support this (Van Riemsdijk, 1979). Extrapolation of the regression equation would thus lead to an over-estimation of the sorption. It can be inferred from Figure 2 that the reaction rate of all experiments decreases strongly with increasing sorption. Assuming that metal phosphates are formed that belong to one of the minerals as identified by Haseman et al. (1950, 1951) with a phosphate to metal ratio ranging from 2 to 1, it follows from the measured sorptions as shown in Figure 2, in combination with the Al + Fe contents of the samples as given in Table 1, that only a fraction of the metal oxides is needed to form these (presumed) metal phosphates. It is thus not unlikely that the decrease of the reaction rate is caused by the formation of a coating of metal phosphates on the metal oxides. The other possibilities mentioned in the preceding section are unlikely for the following reasons; case I is unlikely since the R-value is constant during an experiment after some time, case II is highly unlikely because of the strong decrease of the rate with increasing S, this would imply a highly unlikely reduction of surface area during the experiment. At this stage it is already clear that this type of soil does not follow first order precipitation kinetics (cf. equation 7)). The results furthermore show that potassium has a positive effect on the reaction rate as compared with sodium. These findings are in accord with the results as found from the experiments with gibbsite (Van Riemsdijk and Lyklema, 1980a, 1980b). The presumed precipitation mechanism has much in common with the oxidation mechanism of metals (Evans, 1955; Roberts, 1962; Fehlner and Mott, 1970). Several theoretical rate equations are used to describe the oxidation kinetics of metals. Often it is difficult to discriminate between the different equations on the basis of experimental data. The
-55-

equations that are most commonly used to describe oxidation measurements are of the following types (constant supersaturation) ,

= k.(l)"1 dt ^ = k n (k 1 + k , ) " 1 L z dt

(1)

(2)

Si = k.e'V
dt
l

(3)

Si = k.eV 1
dt
L

(4)
1 is

with 1 the thickness of the surface coating formed. constant surface area. dl/dt is reaction rate. k.

proportional to the amount reacted S, for the condition of (i = 1, 2 or 3) is rate 'constant',

Since the thickness of the presumed coatings cannot be measured all results will be interpreted here as a function of S instead of 1. Some other types of equations, rewritten for conditions of constant c , that have been used to describe phosphate sorption (Enfield et al., 1976; Novak, 1976; Overman and Chu, 1977a; 1977b; Fiskell et al., 1979) are;

^ = k..(k dt ^ = k1Sk2 l dt

- S)

(5)

(6)

= k, dt
-56-

(7)

Some k. parameters will be a function of the super-saturation. The applicability of the different rate equations to the experiments can be tested in the differential form and/or after integration of the respective equations. In fact equation 1 has already been tested in its integrated form (Figure 2). In general the adsorption kinetics will dominate the initial stage of the reaction and thus the first stage of the reaction period should not be included if one wishes to study the applicability of the different rate equations to the precipitation kinetics. The precipitated amount will be equal to, S = S + S - S a , where S represents the measured sorption, S the precipitated amount at the start of the experiment and S a that part of S that should be attributed to an adsorption process. The uncertainty about the values of S and S has no effect on the test of the validity of equations 2, 3, 5 and 7. Using S instead of S_ influences "only1 the value of one of the 'constants' of the respective equations (2, 3 and 5 ) . However, this will cause problems if one wants to know the dependence of the different k.'s on the super-saturation. Equation (1) may only be tested safely by using its integrated form, because then the above-mentioned uncertainty has no influence on its applicability. Equations 4 and 6 may only be tested for the condition that S - S is negligible compared to S, implying that these equations preferably should be tested for higher S values. The reaction rate can be calculated from the measured points of Figure 2, or from recorder curves. in fact a recorder was connected with the burette of the c -stat and P registered the volume of acid required to keep the pH of the system constant as a function of time. With the help of Figure 1 in combination with the known concentrations in the burette, and the soil solution ratio, the recorder curve can be converted to the amount of phosphate reacted per amount of soil as a function of time. On average, 10 different reaction rates were calculated per experiment with this method. Calculation of reaction rates from the data points (Figure 2) would lead to much less data per experiment.
-57-

Equations (1) to (6) were tested with the data from the 5 experiments for t > 1 h. Equations 1 and 2 were tested in the integrated form. The results could best be described by (3) with coefficients of determination (r^) ranging from 0.9 8 to 1.00 for the individual experiments, and second best with 2 (1) (for r values cf. Figure 2 ) . The worst fit was obtained 2 with (5) with r ranging from 0.77 to 0.89. The calculated k- values of (5) are for exp. 1 - 5 : 5.3, 8.9, 9.7, 13.7 and 18.7 mmol/kg, respectively. These are thus the maximum S values as predicted by this equation and are clearly a function of c , whereas the k, value of (5) p 1 is almost independent of c (0.11 0.02). This type of equation is often used (Hornsby and Davidson, 197 5; Enfield et al., 1976; Fiskell et al., 1979) to describe the results of sorption experiments but should not be expected to hold if precipitation occurs (cf. Introduction). Using this equation here may lead to a considerable under-estimation of S for longer extrapolated reaction times (see also Figure 3 ) . For the reasons discussed above, equation 3 has been selected as the best and most convenient rate equation to describe the sorption experiments. This equation is sometimes referred to as the Roginsky-Zeldovich equation (Roginsky and Zeldovich, 1934) or in the integrated form as 'the direct logarithmic equation' (Evans, 1955). It is often found applicable for activated sorption processes (Roberts, 1962). The calculated rate coefficients are shown in Table 2. It can be seen that both k, and k_ are a function of c . It is seen 1 2 p that the value of k_ decreases with increasing c and also decreases if sodium is replaced by potassium (Exp. 4 and 5) . This may be explained by different physical chemical properties of the surface layer formed (e.g. its porosity, surface potential, change in surface area with S etc.). It may be noted that Barry and Stone (1960) also found a decrease of k with increasing oxygen pressure (comparable with c here) for oxidation experiP merits with zinc.
-58-

TABLE 2 CALCULATED VALUES OF k AND k OF (3) BY CURVE FITTING THE CALCULATED REACTION RATES (RECORDER CURVES) OF EXP. 1 TO 5, FOR DETAILS SEE TEXT. k* IS OBTAINED WHEN S* OF FIGURE 1 IS SUBSTRACTED FROM THE DIFFERENT S VALUES PRIOR TO CURVE FITTING Exp. k2 -kg/mmol1.55 2.53 4.1 14.9 7.08 1.31 0.772 0.661 0.564 0.434 0.988 0.979 0.996 0.992 0.991 2 r

l - mmol/kg h-

1 2 3 4 5

13.8 14.0 21.1 91.1 165.6

k, increases with increasing super-saturation but the dependency of k on c is greatly influenced whether or not a correction is applied to S, to obtain an estimate of S . In Table 2, k. is calculated using the total sorption as measured, and by using S* (Figure 1) as a correction term yielding k*- k. is more or less proportional to c (k, = 1 * p 1 a cb o rz =0.94, a = 9.8, b = 0.97) whereas kj is more or less proportional to /cZ c" r 2 = 0.80, a = 3.5, =P (k* <kl = = aac p b = 0.45) for experiments 1 - 4 . More measurements at short reaction times are necessary to evaluate the correction that should be made on S in order to get the real precipitation rate parameter and its dependence on c . In fact a soil that contains even less initial phosphate should be used for this purpose also. The dependency of k_ on c_ for experiments 1 - 4 can best be described with k~ = ac~ (r2 = 0.99, a = 0.23, b = 0.19). The integrated form of (3) for the condition, that S = 0 at t = 0 is, S = k 2 - 1 ln(t +(k ] k 2 )" 1 ) + k 2 - 1 l n k ^ (8)

-59-

Figure 3 shows the sorption as a function of time calculated with the help of (8) and the data in Table 2 for the different experiments (lines) together with the individual measurements (points). Referring to the foregoing discussion on the amount of metal phosphates that can be formed in the soil used, it can be seen that the predicted S values are well below the maximum amount of phosphate that can be precipitated even after ten years reaction time. This maximum, for a metal-phosphatic ratio of 1, would amount to 568 mmol/kg (cf. Table 1). So far the data have been interpreted in terms of amounts reacted per unit mass of soil because the available reactive surface area of the soil is unknown. However, the reactions involved are in fact surface reactions and thus an analysis of the effect of the surface are on the rate constants of equation (s), for example, may be quite useful. The relationship between the measured S value and 1 will be: Alp/M = S (9)

where A is the specific reactive surface area of the soil (area/mass), p the density of the formed surface coating, M the molecular mass of this coating per unit phosphate, 1 and S have already been defined. (3) can now be converted into units of S with the help of (9) leading to, || = k x A A exp (-k2i J S) = k x A X exp (-ka |y) (10)

with p/M = X. For conditions of constant surface area and constant composition of the surface layer AX can be incorporated in the rate 'constants' k and k , as has been done so far. These 'combined' constants can be determined from experiments. The analysis thus shows that the slope of a plot based on (8) is directly proportional with A.
-60-

"dp (mmoi/lh 35-

30-

25-

20-

o 6

e tsto-

oV\f

t hr

1d

7d

30 a

1yr 10 yr Reaction t'ime, t nt

Fig. 3.

Sorption of phosphate on sandy soil at constant c and pH (phosphato-stat) as a function of Int. The experimental conditions are given in Figure 1. The solid lines are calculated with (8), k and k values as calculated from the recorder curves of the c -stat (see text for explanation).

32 Exchange experiments with P The results of the experiments described show that the sorption that is found after a certain reaction time is a function of c . The larger the c , the larger the sorption P P which is measured. The assumed reaction mechanisms is the formation of coatings of metal phosphates on the soil metal oxides through which diffusion has to take place. If this is the case, it is to be expected that the fraction of sorbed phosphate exposed to the solid solution interface is lower the higher the c during the sorption, corresponding with thicker coatings. This effect was estimated by performing exchange experiments with 32P. For this purpose samples were used that had been stored for a long time (months) and exhibited a negligible sorption rate at the time the exchange experiments were done. The results are shown in Table 3.
TABLE 3 THE PERCENTAGE OF TOTAL PHOSPHATE OF EXPERIMENT 1 TO 4 (SEE FIGURE 1 FOR EXPERIMENTAL CONDITIONS) FOUND EXCHANGEABLE WITH 3 2 P AFTER VARIOUS EXCHANGE TIMES Time (days) 1 1 3 7 50 56 69 Number of experiment 2 32 41 59 3 13 21 32 4 10 17 26

It can be seen that the fraction that is exchangeable decreases with an increasing c during the experiment, as expected according to the suggested mechanism, irrespective of the duration of the exchange experiment. Assuming that exchangeable P is plant available suggests that high c values as a result of fertilisation should be limited in order to increase the efficiency of the fertiliser.

62-

CONCLUSIONS It has been shown that the measured R value of the different experiments becomes constant after a short reaction time. This enabled accurate experiments at constant c and pH with the c stat. The reaction rate decreased with increasing P S at constant c during each experiment. The reaction rate of all experiments could best be described with one type of rate equation, after a very short reaction time. These facts are in accord with the presumed reaction mechanism, such as the formation of a coating of metal phosphates. Such coatings are supposedly formed by conversion of the outer layers of the metal oxides into metal phosphates. The Rvalue suggests that sodium and potassium will be part of the reaction product because its value is < 1 (chap. 3) (Beek and Van Riemsdijk, 1979). These sorts of reaction products have been identified in other studies (Haseman et al., 1950; 1951). The reaction rate increases when sodium is substituted by potassium. All these aspects were also found for the experi ments with gibbsite (Van Riemsdijk and Lyklema, 1980a, 1980b) although the rate law was a different one. The batch experiments, not reported here, showed that extrapolations of the c stat experiments with respect to time on the basis of the selected rate equation gives satisfactory results. An important practical advantage of the selected rate equation is that it can also be applied to soils that contain an unknown amount of phosphate at the start of the experiment. It may thus be used for the estimation of the long term sorption capacity of agricultural soils that are found to obey this rate equation.

63

EXPERIMENTS WITH SOILS THAT RECEIVED LARGE AMOUNTS OF PIG SLURRY IN THE PAST Experiments have been started that are aimed at predicting the long term sorption capacity of agricultural soils. In particular, soils that are receiving high amounts of pig slurry are the subject of this investigation. The sorption rate of inorganic phosphate with these soils will be measured at almost constant c . P The experimental method is different from the one used before, insofar as it proved to be impracticable, if not impossible, to keep the phosphate concentration constant on the basis of the OH/P ratio during the reaction. Instead the c is P measured by means of Flow Injection Analysis (FIA) using molybdenum blue as colour reagent (Hansen et al., 1977) and the c is brought to the initial value by means of a phosphate containing burette. Full details of the revised technique will be published elsewhere. These experiments last only one to two days and the sorption capacity for longer reaction times can be estimated from extrapolations of these data. To be able to choose the best extrapolation technique (i.e. rate equation) batch experiments that will last approximately one year will also be performed. Results with three different top soils are shown in Figures 4 - 6 . The content of some elements of these soils at the start of the experiment is shown in Table 4. The extrapolation of the measurements for ten years reaction time is used for calculating the 'saturation time' of the upper 0.3 m of these soils. The saturation time is defined here as the time required to fill up the predicted available long term phosphate sorption capacity over a certain soil depth. The saturation time is of course dependent on the phosphate content of the applied slurry and on the application rate. The results of these calculations are shown in Table 4 for two different slurry application rates.

64-

mmol P/kg

1086] 4210 min 1hr Id 7d 30 d

logt

Fig. 4. Measured sorptions at a c of 5 mmol/1 for soil A as a function of time. The regression line was calculated omitting the first three measurements. Extrapolation of this line leads to 15 mmol/kg for one year reaction time and 17 mmol/kg for a reaction time of ten years.

/iimui

r/

h\y

10 86i

. 42-

10min
F i g . 5.

1hr

^log t

1d

Id

30 d

Measured sorptions at a c of 5 mmol/1 for soil B as a function of time. Extrapolation of the regression line leads to 5 and 6 mmol/kg for a reaction time of one and ten years, respectively.

1614 12 10] 8 64210 min

Fig. 6.

1hr

->tog t

1d

7d

30 d

Measured sorptions for soil C at a c p of 5 mmol/1 ( ) and 0.5 mmol/1 (x). Extrapolation of the regression line at 5 mmol/1 leads to 26 and 29 mmol/kg for a reaction time of one and ten years, respectively. The same at 0.5 mmol/1 leads to 10 and 12 mmol/kg.

TABLE 4
II

THE ELEMENTAL ANALYSIS AS DETERMINED WITH RONTGEN FLUORESCENCE OF THE THREE AGRICULTURAL SOILS. THE CALCULATED 'SATURATION TIME' FOR THE UPPER 0.3 METRE SOIL IS GIVEN FOR TWO DIFFERENT SLURRY RATES (40 t/y and 120 t/y). FOR DETAILS SEE TEXT Soil Fe-0 2 s Si0 2 A1203 P mmol/kg A B C 0.29 0.31 1.81 91.7 94.6 90.2 1.58 1.94 2.45 0.16 0.13 0.17 22 18 24 38 14 68 Saturation time (40 t/y) (120 t/y) y 11 4 18

25

The assumptions used in this calculation were the following: soil density 1 500 kg/m , P uptake by crop 50 kg P20c-/ha/y, phosphate content of pig slurry 4.7 kg P^O^/ton slurry ~ 6.7 10 mol/1 total phosphate. It can be seen that the saturation times differ widely. In effect the soil that already contained the highest amount of phosphate at the start of the experiment has the longest saturation time. However, this soil has also a significantly higher aluminium and especially iron content. The saturation time is thus not only dependent on the phosphate load it received in the past but is also, as expected, strongly dependent on the mineral composition of the soil. The extrapolations still have to be compared with the experiments that will last about one year and which are not yet completed. ACKNOWLDGEMENTS The authors are indebted to B. Eshuis, A.B. Roeloffzen and H.J. Timmenga for technical assistance.
REFERENCES Barrow, N.J. and Shaw, T.C., 1978. Soil Sci., 30, 67-76. -68Effects of solution: soil ratio and J.

vigour of shaking on the rate of phosphate adsorption by soil.

Barry, T.I. and Stone, F.S., 1960. 124-44. Beek, J., 1979.

The reactions of oxygen at dark and Proc. Roy. Soc. (London), A 255, Doctoral thesis Agricultural

irradiated zinc oxide surfaces.

Phosphate retention by Soil.

University Wageningen. Beek, J. and Van Riemsdijk, W.H., 1979. ions with Soil. Elsevier, Amsterdam (p. 259-284). De Bakker, H. and Schelling, J., 1966. Nederland. Systeem voor bodemklassificatie voor Comparison of five Soil Stichting voor Bodemkartering, Wageningen. Interaction of orthophosphate Soil Chemistry Part B. In: G.H. Bolt (ed.).

Enfield, C.G., Harlin, C.C. and Bledsoe, B.E., 1976. Sci. Soc. Am. P r o c , 40, 243-249. Enfield, C.G., 1977.

kinetic models for orthophosphate reactions in mineral soils.

Waste-water phosphorus removal using land application. Physical

Civil Engineering-ASCE: 58-60. Enfield, C.G., Kuo, T.L., Subbarao, Y.V. and Ellis, R., 1977. soils Agronomy Abstracts. (p. 25). Evans, U.R., 1955. discussion. The oxidation of metals. A simplified quantitative Oxidation Reviews of pure and applied chemistry, 5, 1-21. Low-temperature oxidation. Chemical first order kinetic model for phosphate reactions in mineral American Society of Agronomy, Wisconsin

Fehlner, F.P. and Mott, N.F., 1970. of Metals, 2_, 59-99.

Fiskell, I.G.A., Mansell, R.S., Selim, H.M. and Martin, F.G., 1979. Kinetic behaviour of phosphate sorption by acid, sandy soil. Environ. Quality, B_, 599-584. Hansen, E.H., Krug, F.J., Ghoset, A.K. and Ruzicka, J., 1977. by flow injection analysis. Analyst. 102, 714-722. Some reactions of Soils Rapid determination of nitrogen, phosphorus and potassium in fertilisers Haseman, J.F., Brown, E.H. and Whitt, C D . , 1950. J.

phosphate with clays and hydrous oxides of iron and aluminium. Sci., 70, 257-271. Haseman, J.F., Lehr, J.R. and Smith, J.P., 1951. ammonium.

Mineralogical character

of some iron and aluminium phosphates containing potassium and Soil Sci. Soc. Am. P r o c , 15, 76-84. Solution and adsorbed fluometuron Hornsby, A.G. and Davidson, J.M., 1973. and predicted evaluation.

concentration distribution in a water-saturated soil: experimental Soil Sci. Soc. Am. P r o c , 37_, 823-828. -69-

Mansell, R.S., Selim, H.M. and Fiskell, J.G.A., 1977. 102-109. Mehra, O.P. and Jackson, M.L., 1960.

Simulated transSoil Sci., 124,

formations and transport of phosphorus in soils.

Iron oxide removal from soils and

clays by a dithionite-citrate system buffered with sodium bicarbonate. Clays, Clay Minerals, Proc. Natl. Conf. Clays Clay Minerals 7th, Washington 1958: 317-327. Ng Kee Kwong, K.F. and Huang, P.M., 1978. Novak, L.T., 1976. Sorption of phosphate by Nature, 271, 336-338. AIChE symp. hydrolytic reaction products of aluminium. Ser. 166-73, 344-357. Novak, L.T. and Petschauer, F.J., 1979. 8, 312-318. Overman, A.R. and Chu, R.L., 1977a. ratio. A kinetic model of steady state I Effect of soil solution phosphorus fixation in a batch reactor. Water Research, 11_, 771-775. A kinetic model of steady state Ill Effect of solution Overman, A.R. and Chu, F.L., 1977b. reaction. Kinetics of the reaction between J. Environ. Quality, orthophosphate ions and muskegon dune sand.

Transport and reactions of ions in soils.

phosphorus fixation in a batch reactor. Water Research, 11_, 779-781. Metal Oxidation. Roberts, M. Wyn., 1962.

Quart. Rev., London, 16_, 71-99.

Roginsky, S. and Zeldovich, Ya., 1934. monoxide on manganese dioxide. Schwertmann, U., 1964.

The catalytic oxidation of carbon Acta Phys., 1^ 554-594.

Differenzierung der Eisenoxiden des bodens durch

Extraction mit Ammonium oxalaatlosung. Z. PflanzenernShrung Dung. Bodenkunde, 105, 194-202 . Tamm, 0., 1934. Oxalate method in chemical examination of soils. Medd. Stat. Skogsfflrsoksanst., 27. Van Riemsdijk, W.H. and Lyklema, J., 1980a. Colloids and Surfaces, I _ , 33-44. Van Riemsdijk, W.H. and Lyklema, J., 1980b. Sci. (in press) . Van Riemsdijk, W.H., 1979. and a sandy soil. Reaction mechanisms of phosphate with A1(0H) Doctoral thesis Agricultural University Wageningen. Reaction of phosphate with J. Colloid Interface gibbsite (A1(0H),) beyond the adsorption maximum. The reaction of phosphate with aluminium hydroxide in relation with phosphate bonding in soils.

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PHOSPHORUS ANALYSIS IN SOILS A. Cottenie and L. Kiekens State University of Ghent, Belgium.
ABSTRACT Soil application of heavy doses in soils. for estimating both. calibration total and comparison P analysis between rates of results as most slurry of slurries A large and sludges number of of soils. either the has In increased this so-called

the problem of P determination methods has been proposed paper a distinction intensity, capacity, In order obtained indicative and sewage for or

extracting

the P status

is made between methods reflecting

to facilitate the enrichment

in different sludges.

laboratories,

is considered

caused by heavy application

More information determined obtained being by determining

concerning systematically

the P nutrient the

intensity

may be image can be P amount transfer the P significant

as the water soluble by the soil. to the liquid acidified. between soils

fraction.

A more complete 'mobility'

of the total suspension, a levels.

retained

This can be done by observing phase in a soil-water results indicate P enrichment Practical

from the solid progressively difference

being

of various

71-

1. INTRODUCTION During recent decades, phosphorus input in soils has been continuously increased by agricultural practices, as well as by mineral fertilisers, slurries and sludges. Van de Maele (197 5) estimated the average amounts of P applied in bioindustrial farms and made a distinction between P from mineral origin and from slurry. For different crops an important excess of P input resulted from the application of slurry as shown in Table 1.
TABLE 1 P FERTILISER PRACTICES IN BIOINDUSTRIAL UNITS Applied P (kg/ha)^ Crop Slurry Mineral Total Recommended P fertilisa tion rate (kg/ha)

Excess (kg/ha)

Pasture Barley Fodder beet Corn Potatoes

129 116 168 368 111

16 28 28 18 53

145 144 196 386 164

18 33 46 40 46

127 111 150 346 118

At the present time, therefore, the problem of diagnosing the Pstatus of soils is no longer limited to the estimation of fertiliser requirements, but in many cases extended to the characterisation of the accumulation levels. At the same time it may be useful to measure the rate of Prelease into soil and surfacewater, which may take place to an extent that corresponds with water pollution. It is remembered that the guideline of the CEC fixes the maximum phosphate content of surface waters suit able for the preparation of drinking water at 0.4 (class A) to 0.7 (class B) mg P25 P e r ^ T n e s e parameters have been introduced in order to meet ecological requirements (Guideline
72

of 16 June 1975 - Publicatieblad van de EG van 25.7.75, Number L 194/34-39). 2. FORMS OF PHOSPHORUS IN SOILS According to Black (19 68) the phosphorus compounds in soils can be divided into the following three groups: - inorganic compounds in which phosphorus is combined largely with calcium, magnesium, iron and aluminium, and with clay minerals - organic compounds present in plant and animal residues and products of microbial synthesis - organic and inorganic P compounds in the cells of living matter, which in a sense serve as the connecting link between the other two general classes of compounds. They originate almost exclusively from orthophosphate, in which a central P atom is surrounded by and bound to four oxygen atoms. In the inorganic forms, one to three hydrogen ions of phosphoric acid are replaced by metallic cations. In organic forms, one or more hydrogen ions are eliminated in an ester linkage and the remaining ones are replaced partly or completely by metallic cations. 3. AVAILABILITY OF SOIL PHOSPHORUS AND PARAMETERS AFFECTING IT Crops normally take up H-PO." ions derived mainly from inorganic P held in amorphous, non stoechiometric complexes with Fe and Al oxides, humates and clay minerals, and from easily acid soluble compounds, mainly calcium phosphates (Williams, 19 62). Together these constitute only a small and variable portion of the total soil P and up to one half or more may be organic, especially in acid soils. Mineralisation of organic P may release important amounts of inorganic P in favourable conditions of moisture and pH, root activity including rhizospher and mycorrhizae.
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In this way organic P reserves may contribute appreciably, while inositolhexaphosphate, the main organic form so far identified, can also act, indirectly by combining with active Al and Fe which otherwise immobilise inorganic P. According to Mattingly (1965) P release is characterised by three parameters: capacity (buffering characteristics), intensity (concentration) and kinetics (rate). The intensity characteristics of a soil will determine the initial concentration of P, while its capacity reflects the ability of a soil to maintain this concentration by buffering against the withdrawal of P from the soil solution by roots. Since the amount of P in the soil solution at any one time is very small, and plants growing in the soil apparently absorb P only from the soil solution, the latter must be renewed several times each day during the growing season (Barber, 1962). The factors involved in renewal of the soil solution are the amount of P which can be solubilised, its degree of solubility, and the rate of its diffusion from the solid surface to the plant root surface. The mobilisable P reserve or the capacity factor can be equated with the pool of labile, isotopically dilutable inorganic P, directly measured by the so-called 'L' or 'A' value obtained from plant experiments with radioactive P. Repeated extraction of a soil sample also provides information about the mobilisable P pool. Table 2 shows the concentration of different nutrient elements found in successive saturation extracts of two soils, intensively fertilised with animal waste products. The transfer of phosphate to the soil solution increases progressively and reaches a maximum when the largest amounts of Ca are eliminated. The high P concentrations in these extracts may be explained by the presence of organic complexing

74-

agents, which by means of complexation with Ca, Fe and Al prevent these ions from forming insoluble compounds with phosphates.
TABLE 2 CONCENTRATION OF NUTRIENT ELEMENTS IN SUCCESSIVE SATURATION EXTRACTS OF TWO INTENSIVELY FERTILISED SOILS Successive extractions 1 1. Sandy soil P K Mg Na 2. Sandy loam soil P K Mg Na (mg/1) 2.86 24.13 5.05 3.92 3.90 4.70 14.CO 3.40 2.28 2.82 5.64 4.05 1.93 0.72 1.94 8.36 4.97 1.76 0.84 1.75 8.72 4.63 1.84 0.81 1.67 8.58 5.55 1.75 0.92 1.63 8.50 4.56 1.66 0.76 1.37 7.85 4.08 1.47 0.62 1.37 Ca (meq/1) (mg/1) 11.66 4.48 2.15 1.36 1.29 16.15 2.63 1.65 0.71 0.86 18.OO 1.64 1.36 0.43 0.58 18.35 2.02 1.39 0.48 0.64 16.81 1.91 1.39 0.43 0.57 16.17 2.35 1.29 0.55 0.72 17.38 2.48 1.17 0.47 0.62 15.91 1.53 1.03 0.26 0.51 Ca (meq/1) 2 3 4 5 6 7 8

In normal conditions of not excessively enriched soils, soluble P is much lower and seldom exceeds 2 mg P per litre in the saturation extract. 4. AVAILABLE AND EXTRACTABLE P CONTENT OF SOILS A large number of methods have been proposed for the assessment of plant available P. Most of the methods are based on extraction procedures and differ according to the nature, concentration and pH of the solvents used, the soil : solvent ratio, the extraction time and temperature. These determine the strength of the extraction and the extent to which the values can be regarded as reflecting capacity or intensity.
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TABLE 3 CHARACTERISTICS OF SOME EXTRACTION METHODS USED FOR THE DETERMINATION OF THE P-STATUS OF SOILS Method Extraction solution 0.025n HC1 0.03 n NH F pH 3.5 O.ln HC1 0.03 n NH.F 0.5 n H 2 S 0 4 1% citric acid NH.-lactate pH 3.75 0.2 n NH oxalate

Soil/solution ratio

Extraction period

Bray and Kurtz (1945) Bray and Kurtz (1945) Dean (1938) Dyer (1894) Egner et al. (1960) Joret and Herbert (1955) Lakanen and Ervifl (1971) Mehlich (1953)

1/7 to 1/5

40 sec to 5 min

1/7 1/50 1/10 1/20 1/25 1/10 (v :v) 1/5 (w :v) 1/4

40 sec 1 h 2 h + 24h+lh 4 h 2 h 30 min 5 min

0.5n NH 4 0Ac + 0.02M EDTA pH 4.65 0.25n H SO 0.05n HC1 pH 1.2 0.2n NH CI - 0.2 n HOAc (0.015nNH4F 0.012n HC1) pH 2.5 NaOAC + HOAC pH 4.8 0.5 M NaHCO, pH8.5 NaAc + HAC pH 4.8

Mehlich (1978) Morgan (1941) Olsen et al. (1954) Peech and English (1944) Soltanpour and Schwab (1977) Truog (1930) Van den Hende and Cottenie (1960) Van der Paauw and Sissingh (1971) Vuorinen and Makitie (1955)

1/10 1/2 1/20 1/5

5 min 30 min 30 min 30 min 15 min 30 min 30 min 1 h 1 h

1M NH 4 HC0 3 +0.005M 1/2 DTPA pH 7.6 0.002 n HSO. 2 4 NH Ac + HOAc pH 4.8 Water 0.5 n NH OAc pH 4.65
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1/200 1/2 1/60 1/10

According to Williams (1962) the intensity factor is likely to be more critical in soils of widely varying P retention capacity and when the quantity of labile P is intermediate. Conversely, capacity measurements are more likely to be adequate when the P retention capacity is fairly constant and where the labile P is high or low. In very poor soils even the total P may be useful. Most extractants used in soil testing were developed empirically and vary between pure water and strong solvents. Some extractants are rather specific for certain P compounds in the soil. On the other hand a number of methods have been proposed for simultaneous extraction of phosphorus and other nutrient elements. The main characteristics of some extraction methods used for the determination of the P status of soils are summarised in Table 3. 5. SIGNIFICANCE AND DETERMINATION OF TOTAL P IN SOILS The possible P enrichment of soils caused by landspreading of slurry and sewage sludges is not particularly related to a specific fraction, but results in a general increase. The added P is distributed over the different chemical forms in function of local and accidental conditions. Therefore the 'CEC-Workshop on Standardisation of analytical methods for manure, soils, plants and water' held in Ghent in June 1978i proposed the determination of total P in order to observe soil enrichment with P and to make nutrient balances. The method of De Haan (Agricultural University, Wageningen) was adopted for this determination and its principle is as follows: The soil (air dried soil < 2 mm, ground in a vibrating mill with beakers and balls made of tungsten carbide to < 0.05 mm), is digested with Fleischmann's acid. The digestion temperature of 140 C is not critical and may vary between 120 - 160 C. Together with orthophosphates, molybdates form in acid medium, a yellow compound H-jP (Mo-,0-,0) ., which can be reduced to the
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phosphomolybdenum-blue complex. Sb is added to catalyse the formation of the phosphomolybdenum-blue complex to its endpoint. This method, as well as an alternative procedure, proposed by Professor H. Kick, is described in the addendum. 6. ANALYTICAL CHARACTERISATION OF P-ENRICHMENT OF SOILS BY INTENSIVE FERTILISATION AND SLURRY APPLICATION Especially in the case of phosphorus, soil nutrient status is normally expressed in terms of 'available' fractions. Moreover, phosphorus is specifically an element which canbe stored in the soil without considerable risk of loss by leaching. For this reason, high rates of P-fertilisation in the preceding years, have led to a continuous increase of the P content of many soils. Slurry and sludge applications have more recently intensified this evolution. Such enrichment of the soil clearly appears in its total P-content as shown in Table 4.
TABLE 4 TOTAL P CONTENT OF THREE SOILS, WITHOUT AND WITH APPLICATION OF HEAVY DOSES OF PIG SLURRY Soil texture Total P content (mg/kg) Not treated Sandy Sandy loam Heavy clay 340 340 725 Treated 500 510 900

The already high level in the soils not treated with slurry, are considerably increased after such treatments. On the other hand a variable part of this total Pcontent may be fixed in a more or less strong way. Here it is useful to distinguish between the well known nutrient capacity and intensity. This can be done by comparing the total contents with the amount soluble at the pH of the soil, this means in the soil solution or in a water extract.
-78-

Even more complete information can be obtained by determining systematically the 'mobility' of the total P amount being retained by the soil. This can be done by observing the P transfer from the solid to the liquid phase in a soilwater suspension, being progressively acidified. Table 5 shows the results obtained by equilibrating soil water suspensions (ratio 1 : 5) during 30 minutes at different pH values down to pH 0.5. The pH was controlled by addition of appropriate amounts of HN0, using a pHstat apparatus (see also Figure 1 ) .
TABLE 5 MOBILITY OF P as FUNCTION OF pH P solubilised (mg/kg soil) 4.15 5.15 18.70 145.25

Soil texture

pH adjusted

pH filtrate

% of total P

Sandy soil (not treated with slurry)

pH soil 4 2 0.5

5.5 4.0 2.1 0.7

1.2 1.5 5.5 42.7

Sandy soil (treated)

pH soil 4 2 0.5

5.8 4.0 2.1 0.7

8.30 20.75 56. OO 226.20

1.7 4.2 11.2 45.2

Heavy clay soil (not treated)

pH soil 4 2 0.5

7.0 4.3 2.4 0.8

6.20 47.70 76.80 307.10

0.9 6.6 10.6 42.4

Heavy clay soil (treated)

pH soil 4 2 0.5

7.2 3.2 2.5 0.8

8.30 89.20 120.40 315.40

0.9 9.9 13.4 35.0

Only some 1% of the total P was found in the original solution at soil pH while 35% to 40% was mobilised and passed into the solution at pH 0.5. The mobilisation of treated and non treated soils appears to give significantly different
79

HEAVY CLAY SOIL

: TREATED : NOT TREATED

PH

0.5

F i g . 1.

Mobility of P as function of pH i n a sandy and heavy clay s o i l t r e a t e d and not t r e a t e d with s l u r r y

patterns and this is of course more pronounced when compared with soils of normal or lower P accumulations. 7. CONCLUSIONS AND GENERAL REMARKS The CEC-expert group on analytical methods has proposed considering total soil phosphorus as most indicative for the enrichment caused by heavy application rates of slurry and sewage sludges. By this proposal the working group intended to recommend a reference method with the aim of a better possibility for calibration and comparison between results obtained in different research centres. At the same time it was strongly recommended to standardise at least the way of expression of the results in order to avoid confusion and to prevent the necessity of permanent recalculations. Thus the P contents are given in terms of the element and not of its oxide, and expressed in mg per kg soil. For obtaining more information concerning the actual situation of availability it is stressed that the P nutrient intensity of the soils under study may be determined as the water soluble fraction. At the same time this gives an indication of possible leaching and surface water enrichment with phosphates. Furthermore an experimental technique is described for the determination of P-mobility in the soil by observing its solubilisation pattern in function of decreasing pH. Practical results indicate a significant difference between soils of various P enrichment situations.

81

8. ADDENDUM: DETERMINATION OF TOTAL P IN SOILS a) Method recommended by the CEC working party (197 8) Reagents Sulphuric acid (d = 1.84) Nitric acid (d = 1.40) Fleischmann's acid: mix equal volumes of H 2 SO. (d = 1.84) and HNO3 (d = 1.40). Prepare by adding small amounts of the H 2 S0 4 , while cooling, to the HN0 3 (d = 1.40) Sulphuric acid 0.9 m: 5 ml H 2 S0 4 (d = 1.84)/100 ml

Sulphuric acid 2.5 m: 70 ml H 2 S0 4 (d = 1.84)/500 ml Ammoniummolybdate: 20 g (NH.),Mo024.4 aq/500 ml. in hard glass. Store in dark Ascorbic acid 0.1 m: 0.889 g ascorbic acid/50 ml. Prepare fresh daily Potassium antimonyltartrate 0.274 g KSbOC4H4Og/lOO ml Mixed reagent: in the sequence mentioned mix 50 ml sulphuric acid 2.5 m, 15 ml ammonium molybdate, 30 ml ascorbic acid, 5 ml potassium antimonyltartrate. Prepare just before use Diluted mixed reagent: dilute 20 ml of the mixed reagent to 100 ml with water. Prepare just before use Carborundum beads Standard solution 60 ppm P: 0.2631 g KH2P04/litre (volumetric flask) Standard series Pipette 0.0 - 10.0 - 20.0 - 30.0 - 40.0 - 50.0 ml of the standard solution into 100 ml volumetric flasks. Add 10 ml of cone, sulphuric acid solution and make up to the mark with water. Keep

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Procedure Weigh 2.50 g of air dry soil into a dry 100 ml volumetric flask. Add 20 ml Fleischmann's acid and mix; add a few carborundum beads. Digest on a hot plate for one hour at a temperature of about 140C. Then digest at a high temperature to a white colour or until the colour ceases to change. Let cool and make up to mark with water. Filter. Prepare a control also. Dilute the standard series, the samples and the control 5 times with water. Pipette from these diluted solutions 1.0 ml into test tubes and add 5.0 ml of the diluted mixed reagent. Shake and wait 20 minutes at least. Measure (1 cm cuvette) the extinction at 720 nm. The standard series has a concentration in the final solution of: 0 - 0.2 - 0.4 - 0.6 - 0.8 - 1.0 ppm P. Calculation P (mg/1 000 g soil) = (a - b) x 1 200 in which: a = ppm P measured in the sample b = ppm P measured in the control. Remarks 1. 2. The colour is stable for at least 5 hours. 5+ Only As will interfere which can be prevented by 3+ reduction to As by adding, before the addition of the diluted mixed reagent, a few ml of a reduction mixture containing 10 ml sulphuric acid 2.5 m + 20 ml sodium-metabisulphite (10 g Na2S20r/100 ml) + 20 ml sodium-thiosulphate (1 g Na 2 S 2 0 3 .5 aq/100 ml) + 270 ml distilled water. Prepare just before use. De Haan, Agricultural University - Wageningen (CEC Workshop on Standardisation of Analytical Methods - Gent, June 1978).

Source:

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b) Alternative method Reagents Aqua regia: mix 3 parts concentrated HC1 with 1 part concentrated HNO3 dissolve 1 g methol (monomethyl-paraaminophenol sulphate), 5 g Na2S03.7 ag and 150 g NaHS03 (or 137 g Na 2 S 2 0 5 ) in 1 I dissolve 50 g NH. molybdate in 200 ml H 2 0, add 140 ml concentrated H 2 S0 4 , bring to 1 I dissolve 340 g NaAc.3 aq (or 205 g NaAc.O aq in 1 1 H20)

Scheel I:

Scheel II: Scheel III:

Stock solution 500 ppm P: dissolve 2.1965 g KH 2 P0 4 0 aq in 1 I H 2 0. Prepare a standard series of 0 - 5 - 15 - 25 - 35 ppm P in water. From each standard solution 10 ml is taken and treated in the same way as the sample. Procedure Mix 10 g air dry soil with 50 ml aqua regia in a boiling flask equipped with a reflux condenser and ground joint. Keep the mixture overnight. Heat gently for 2 hours using the reflux condenser. Filter into a 200 ml volumetric flask and wash the filter with hot water. Make up to the mark. Pipette 10 ml extract into a 100 ml volumetric flask, add successively 30 ml H 2 0, 10 ml Scheel I and 10 ml Scheel II solution. Shake carefully and after 15 minutes add 20 ml Scheel III solution. Bring the volume to 100 ml and shake. The absorbance is measured after 15 minutes at 700 nm. Quote the results as mg P/kg soil. Remarks For the determination of P in calcareous soils, the reagent Scheel II is prepared with HNOj (400 ml) instead of sulphuric acid (140 ml), in order to avoid precipitation of CaSO,. Source: Professor Dr. H. Kick, Bonn (FAO European network on trace element research).
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REFERENCES Barber, S.A., 1962. Black, C.A., 1968. A diffusion and mass-flow concept of soil nutrient Sci., 93_, 39-49. 2nd Ed. John Wiley & Sons, Soil-plant relationships.

availability. Soil Inc. p. 558-644.

Bray, R.H. and Kurtz, L.T., 1945. Dean, L.A., 1938. Dyer, 1894.

Determination of total, organic and Soil Sci., 59, 39-45.

available forms of phosphorus in soils. J. Agri. Sci., 28_, 234. Journ. Chem. S o c , T 65, 115.

Egner, H. , Riehm, H. and Domingo, W.R. , 1960.

Untersuchungen tlber die

chemische Bodenanalyse als Grundlage fur die Beurteilung des Nahrstoffzustandes der Bflden. II. Chemische Extraktionsmethoden zur Phosphor- und Kaliumbestimmung. Kgl. Lantbrukshflgak. Ann., 26, 119-215. Joret, G. and Herbert, J., 1955. Lakanen, E. and Ervio, R., 1971. J. Ann. Agron., , 233. A comparison of eight extractants for

the determination of plant available micronutrients in soils. Acta Agr. Fenn., 123, 223-232. Mattingly, G.E.G., 1965. The influence of intensity and capacity factors Min. Agr. Fisheries and North on the availability of soil phosphate. Food (London) Tech. Bull., 13, 1-9. Mehlich, A., 1953. Mehlich, A., 1978. Determination of P, Ca, Mg, K, Na and NH . Carolina Soil Test Division, Raleigh, N.C. (Mimeo, 1953). Influence of fluoride, sulfate and acidity on extractable Commun. in soil phosphorus, calcium, magnesium and potassium. science and plant analysis, 9 _ , 455-476. Morgan, M.F., 1941. system. Chemical soil diagnostic by the universal soil testing Estimation Connect. Agric. Exp. Sta. Bull., 450.

Olsen, S.R., Cole, C.V., Watanabe, F.S. and Dean, L.A., 1954. OS Dept. Agr., Circ. 939. Peech, M. and English, L., 1944. 5 J 7 _ , 167. Soltanpour, P.N. and Schwab, A.P., 1977.

of available phosphorus in soils by extraction with sodium bicarbonate. Rapid microchemical soil test. Soil Sci.,

A new soil test for simultaneous Soil

extraction of macro- and micronutrients in alkaline soils. Sci. and Plant Analysis, 8 (3), 195-207.

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Truog, E., 1930. soils.

The determination of the readily available phosphorus of

J. Amer. Soc. Agron., 2_2, 874-882. Etudes des principes et methodes

Van den Hende, A. and Cottenie, A., 1960. d'analyse chimique du sol

et des vegetaux. C.R. Rech. Trav.,

Centre Chim. et Phys. Agr., IRSIA, 25. Van de Maele, F., 1975. intensif. Fumures pratiquees dans des exploitations d'elevage

Revue de l'Agric, 6 _ , 1487-1494. An improved method of water

Van der Paauw, F. and Sissingh, H.A., 1971.

extraction for the assessment of availability of soil phosphate: Pw value. Versl. landbouwk. onderzoek, 749. Vuorinen, J. and MSkitie, 0., 1955. Finland. The method of soil testing in use in

Agroged. Publ., 63, 1-44. C hemical soil tests as an aid to increased Trans. Intern. Soil Conference New Zealand, Comm.

Williams, E.G., 1962. productivity. IV and V.

86-

DISCUSSION T.W.G. Hucker (UK) I would just like to make one comment - I am very pleased to hear the emphasis on expression of phosphorus in terms of P. There has been much confusion over the years and standardisation is going to help a lot. We have spent hours discussing mg/kg against ml/kg in the UK and I feel sure this is not the place to raise that issue. A.E. Johnston (UK) May I ask Professor Cottenie to amplify a point in one of his Tables. It was headed, 'Successive Saturation Extracts' (Table 2 ) . Can you just say what you mean by 'successive saturation' and what method you actually used? A. Cottenie (Belgium) The soil is put in a vessel and water is added until complete saturation is achieved. That means that there is no water on the surface, all the pores are filled with water. After an equilibration time of one day, water is extracted by suction; it is dried and then the whole process repeated 8 or 10 times. It is a classic method of making a saturated extract, for example, for measuring electrical conductivity and total salt content.
R. Gerritse (Netherlands)

Is the water that is extracted from the column in this way analysed as such or do you have a centrifugation procedure prior to analysis? A. Cottenie It is analysed as such. R. Gerritse The water extracted from the column in this way might contain a lot of particulate matter.
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A. Cottende We have studied that problem. This is what one miqht call a 'pseudo' solution and not a real solution. So maybe there is some chelated material in the solution but in acidifying it we could see what was released from the chelates and it was not so much phosphorus but trace element - heavy metals.
S. Gupta (Switzerland)

You showed us a method of mobilising phosphorus as a function of soil pH. Bearing in mind that the soil pH is not decreasing, can you give us another method for determining the mobilising with phosphate? A. Cottenie If you look at the general equilibrium in the soil, it is established at the pH of the water in the soil. In these conditions quite an amount, not only of phosphorus but of all elements, is being retained by the solid phase. If you want to know what is mobilisable, as opposed to mobile at that time, in function of time and changing external conditions, you can manipulate a lot of different techniques such as successive extractions, or more and more aggressive solutions. You can change redox potentials and so on. You can put all this in equations. The pH is always one of the variable factors present in the equation giving the concentration of an element in the soil solution as a function of the factors acting on it - even redox potentials. It has been shown that pH and redox potential expressed in function of electron concentration introduces a new concept: pe + pH. It has also been shown theoretically as well as experimentally that this is a constant value in a given soil. So pH is always the most important factor in determining the total influences acting on the mobility of an element. We have chosen pH changes in order to follow the way in which a stored element is mobilisable. On the other hand, if you make a soil extract with water, you do it at a pH of 6 or 7, but in the rhizosphere you have pH values between 3 and 4 for different plants.
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SESSION II PHOSPHORUS IN WASTES (CONTENTS, CHEMICAL FORMS, ETC.) Chairman: A. SUss

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PHOSPHORUS CONTENT OF SLUDGE FROM SWISS SEWAGE TREATMENT PLANTS O.J. Furrer and R. Bolliger Swiss Federal Research Station for Agricultural Chemistry and Hygiene of Environment, 3097 Liebefeld-Berne, Switzerland. ABSTRACT The P-aontent steadily increased of P-elimination per kg dry matter without P-elimination P-elimination with in sludges in the last chemicals: from Swiss wastewater few years 1971: average treatment plants has

due to a progressive of sludge from

introduction 27 g P plants with

11 g, 1979: average

(DM). In 1978/79 the P-content The highest of

amounted to 17 (2 to 46) g P/kg DM, from plants P-content in sludge superphosphate.

36 (9 to 79) g.

(79 g P =

18% P , 0 J was found as high as that The P-solubility that sludge of basic slag. is due to its in citric On average, P-content.

acid

(2%) is found to be 85 7%, close value of sewage

to

70% of the fertiliser

-91-

INTRODUCTION Sewage sludge is a source of plant nutrients: phosphorus, nitrogen, calcium and magnesium. The fertiliser value is mainly due to the P-content, especially in sludges from wastewater treatment plants using chemicals for P-elimination. The N-content is less important except in sludges with a very high water content. The K-content is negligible. In a large number of samples of sludge from Swiss wastewater treatment plants, the P-content was determined. The results are presented and discussed in this paper. PHOSPHORUS CONTENT OF SLUDGES The P-content of sewage sludges has steadily increased in the last few years. 1971 1972 1973 1974 1975 1976 1977/78 1978/79 11 14 17 16 20 23 26 27 g g g g g g g g P/kg P/kg P/kg P/kg P/kg P/kg P/kg P/kg DM DM DM DM DM DM DM DM ( 10 samples) ( 90 samples) ( 50 samples) (93 samples) (241 samples) (272 samples) (392 samples) (435 samples)

This augmentation is certainly due to a progressive introduction of P-elimination with chemicals in the wastewater treatment plants: - without P-elimination: 1977/78 (184 samples): 16.5 g P/kg DM (3-41) 1978/79 (216 samples): 16.8 g P/kg DM (2-46)

-92-

- with P-elimination: 1977/78 (224 samples): 39.5 g P/kg DM (12 to 74) 1978/79 (219 samples): 36.3 g P/kg DM ( 9 to 79). Figures 1 and 2 show the range and the distribution of P-contents of both types of sludges. P-APPLICATION WITH RECOMMENDED DOSES The Swiss advisory board for sludge application recommends sludge doses per ha containing 50 kg available nitrogen, but 3 the dose is limited to 75 m /ha and 100 kg P/ha. Recommended doses per ha for sludges from plants without chemical :al P-elimination z amount to: 47 (20 to 75) m , 2.9 (1 to 5) t DM, 45 (17 to 83) kg P. Recommended doses per ha for sludges from plants with :al P-elimination an chemical amount to: 34 (11 to 60) m , 2.2 (lto4) t DM, 80 (40 to 100) kg P. The normal P-requirement of crops is in the range of 30 to 40 kg P/ha/year. In most cases, excess of P is applied in the form of sludge as compared to the need of crops during one year. In order to avoid P-overfertilisation, the recommended sludge dose should not be applied every year. THE SOLUBILITY OF SLUDGE PHOSPHORUS A method to evaluate the availability of phosphorus often used for fertilisers, especially for basic slag, is extraction with citric acid (2%). In a series of 57 sludge samples, the citric acid soluble P was determined (Figure 3) and found to be on average 85% ( 6.8). In Switzerland, in basic slag, a minimum of 80% of P-solubility in citric acid is required. The P-solubility is
-93-

WITHOUT

P-EL1MINATION

WITH P - E L I Ml NATION

"To

3o

?0

lo

"

So

/ I1

P-CONTENT OF SEWAGE SLUDGES ( g P/KG DM)

Fig. 1. P-content of sewage sludges (CH, 1977/78, 392 samples)

100

WITHOUT P-ELIMINATION 80 (216 SAMPLES) WITH P-ELIMINATION (219 SAMPLES)

j 60 "t

<
to

40 -

20 -

I70 P-CONTENT OF SEWAGE SLUDGES (g P/KG DM)

F i g . 2.

P-content of sewage sludges (CH, 1978/79, 435 samples) p r e s e n t e d in cumulative curve.

100 15 -

10 Ul
Q.

_1 < en (r. ui m

u. o

Y=75, 02 + 0, 34X N = 57 R = 0 , 62

D Z

Hh
Fig. 3.

70 80 90 P-SOLUBII_ITY(/ 0 )

100

40

50

60

P-solubility ( % ) of 57 sludge samples represented in histogram (CH, 1980).

Fig. 4. Relationship between P-content and P-solubility.

P/KG D M

higher in samples with higher P-contents (Figure 4 ) . A significant correlation between P-content (x) and P-solubility (y) was found: y = 75 + 0.34 x (r = 0.62). The P-solubility is higher in sludges from plants with P-elimination: without P-elimination: 83% ( 6) with P-elimination: 90% ( 4 ) . THE FERTILISER VALUE OF SEWAGE SLUDGE The average fertiliser value of sewage sludges in Switzerland can be calculated as follows (N* = available N ) : 1 t DM = 26 kg P at Fr. 2.40 = 19 kg N* at Fr. 1.20 = 3 kg K at Fr. 0.65 = Total = Fr. 62.Fr. 23.Fr. 2.Fr. 87.-

Seventy percent of the total fertiliser value of sludge is due to its P-content. The fertiliser value of 1 m (6% DM) is approximately Fr. 5.-. Over 90% of the fertiliser value of dewatered (25% DM) sludge from wastewater treatment plants with P-elimination is due to the P-content: 1 t DM = 50 kg P at Fr. 2.40 = 5 kg N* at Fr. 1.20 = 3 kg K at Fr. O.65 = Total = Fr. 120.Fr. 6.Fr. 2.Fr. 128.-

In Switzerland the following amounts of P were applied: animal wastes mineral fertilisers sewage sludge 30 000 t/year 20 000 t/year 3 000 t/year.

-97-

DISCUSSION M. Webber (Canada) Your first graph showed that phosphorus in sludges was in creasing with time. D o you have an explanation for this? O.J. Furrer (Switzerland)

Yes, it is due to progressive increase of phosphorus elim ination. J.S.V. McAllister (UK) Are you doing your phosphorus elimination treatment on the raw sewage or are you doing it on the effluent? O.J. Furrer The method we use is normally simultaneous precipitation. However, sometimes the ion is added at the beginning, sometimes at the beginning of aeration or sometimes at the end of aeration. There are different methods. H. Tunney (Ireland)

You showed solubility figures of about 80% for the phosphorus in the sludges. Is that solubility in water? O.J. Furrer No, that is solubility in 2% citric acid; we take 1 g dry matter/100 ml.

98

THE CONTENT OF PHOSPHORUS IN THE SLUDGE OF WALLONIAN WATER PURIFICATION PLANTS AND THE FORM OF PHOSPHORUS IN THESE G. Hanotiaux, J.-P. Heck, M. Rocher, L. Barideau and 0. Marlier-Geets Faculte des Sciences Agronomiques de l'Etat, Gembloux, Belgium.
ABSTRACT The sludge industrial degree element: istics of total produced by four purification chemical plants treating of and urban of view of this soluble 1978) sludge its tendency P is the best on the characterthat has a and/or the

wastewater P related P.

has been characterised

from the point combinations matter analytical

P and of the different to Al, Observations

to Fe, to Ca, to the organic of these It for various (September agricultural out over a year a month. material

and exchangeable at the rate can provide degree related to fluctuate complement represented contrary

have been carried very interesting P, bearing matter,

1977 to September purposes due to

of one sampling

has been established the degree

of total

in mind however that while the mineral

both in space and in time. to these is that figures. relating The mineral P to Al, present. carried

From 15 to 35% of total fractions represent which is combination

to organic

the one relating

P to Fe being

absent

or faintly with

By analogy synthetic organic P similar

experiments generally that

out by means of natural a level for organic N in the

and of sludge participates

phosphate

minerals to that

and by applying accepted more or less

of mineralisation

(20%) , one can estimate in the phosphate nutrition

20% of P in the sludge species.

of vegetable

-99-

INTRODUCTION The sludge produced by four purification plants situated in Wallonia has been characterised from the point of view of the degree of total P by observing in each centre the development of this content over a period of time (Heck et al., 1978). In an attempt to specify the fertilising values of P, it has been judged of interest to determine the various chemical combinations in which this element is implied. These different combinations have indeed proved to be partially accessible to cultivated species, each in a different manner depending upon the kind of species, according to the experiments carried out by the Commission for the Study of Chemical Fertility in the Soil (Comite pour 1'Etude de la Fertilite Chimique du Sol (IRSIA))(Heck and Hanotiaux, 1974; 1976). CERTAIN CHARACTERISTICS RELATIVE TO THE CENTRES The four centres which concern us are situated respectively in the provinces of Luxembourg (Bastogne), Namur (Fleurus and Rhines) and in the province of Liege (Saive). Apart from Rhines, they deal essentially with urban wastewater. At Rhines the principal concern is the treatment of industrial wastewater coming mainly from a cheese factory (Kraft). ANALYTICAL METHODOLOGY The total form of P was determined by an extraction using perchloric acid and the colorimetric method with the reagent nitro-vanado-molybdic. The different mineral combinations of P were determined by applying to the sludge a method which fractionates the mineral P of the soil, inspired from the method used by Chang and Jackson (1957) and perfected by Hanotiaux (1964).

100-

This method consists of letting a series of reagents work successively on the same sample, each reagent being a specific extractor of a mineral combination of P. The following extractants were used: NH.C1 (N) extracting soluble P and exchangeable P (Fraction 0) NH F (0.5 N) extracting P related to Al (Fraction A) NaOH (0.1 N) extracting P related to Fe (Fraction B) H_S0. (0.5 N) extracting P related to Ca (Fraction C ) . Its application to the sludge necessitated a preliminary extraction of fats by sulphuric ether, these fat elements being responsible for the cloudy layers floating on the surface, and thus of loss of substance during the successive centrifugations. This extraction was achieved by submitting the trial sample (1 g) to three successive rinses with 30 ml of sulfuric ether. The ether extracts were eliminated. This elimination has never led to losses of P higher than 0.5% of total P of the trial sample. As regards the fraction P combined with the organic matter, it was determined by establishing the difference between total P and the sum of the various mineral fractions. RESULTS AND DISCUSSION Table 1 groups the average results obtained over the observation period (September 1977 to September 1978, one sample a month) for each centre and for each fraction. These average results are given in absolute values in mg P_0(./100 g DM (AV) accompanied by their coefficient of variation (CV%)* and in percentage of total P. cv% a x lob x
- 101-

TABLE 1 DIFFERENT FORMS OF P IN THE SLUDGE. Fractions P Centres Fleurus Saive Rhines Bastogne AV 913 109 1 218 140 0 CV% 14.46 50.46 13.79 17.14 %TP 15.0 5.2 13.5 5.4 AV 2 442 555 3 477 704 (RESULTS EXPRESSED IN mg P O /lOO g DM (AV) ) A CV% 17.90 14.59 24.33 7.67 %TP 40.0 26.6 38.6 27.2
t

B AV 206 385 33 557 CV% 37.86 25.71 24.24 11.85 %TP 3.4 18.4 0.4 21.5 AV 1 619 301 2 712 434

C CV% 29.59 12.62 55.35 8.53 %TP 26.6 14.4 30.0 16.7

TABLE 1 (Continued)

Fractions Centres Fleurus Saive Rhines Bastogne AV

E O,

A, B, C CV% 14.46 13.34 30.03 7.79 %TP 85.0 64.6 82.5 70.8 AV 917 737 1 574 757

Organic CV% 26.28 34.87 19.06 21.53 %TP 15.0 35.4 17.5 29.2 AV

Tot al P CV% 12.10 13.70 27.04 9.26 %TP lOO 100 100 1O0

5 180 1 349 7 440 1 835

6 097 2 087 9 014 2 592

Note: CV% = coefficient of variation of the various values observed during the control period (September 1977 September 1978) %TP = % Total Phosphorus

As far as total P is concerned, the figures show that the sludge is composed of material which contains a degree of total P ranging on average from 2 100 to 9 000 mg P205/100 g dry matter, which can amount to deposits of P^O,- for the spreading of sludge in the region of 100 m 3/ha, containing about 5% of dry matter, ranging from 100 to 450 kg of P,05/ha. The sludge at Rhines gives, as a rule, the highest content and a very great dispersion of the results (CV% = 27.04). The sludge at Fleurus occupies an intermediary position with an average content of P in the region of 6% of P-O^/dry matter. The sludges at Saive and Bastogne have similar quite low contents, in the region of 2 to 2.5% of P-O^/dry matter. With regard to the various fractions, Table 1 shows the unequal distribution of these depending upon the origin of the sludge. Indeed, fraction 0 represents from 5 to 15% of total P depending on the source, fraction A from 27 to 40%, fraction B from 0 to 22%, fraction C from 15 to 30%. The sum of these various fractions can represent between 65 to 85% of total P, the organic fraction representing the complement to these figures, which is from 15 to 35% of total P. How should one estimate the accessibility of the various forms of P present in the sludge for the crops? As far as the mineral fractions are concerned, one can only estimate it by comparison with the soil or by means of experiments using vegetation vases which have clearly shown the participation of synthetic and natural mineral forms of P, entirely crystallised, in the mineral phosphate nutrition of various vegetable species. Certain research workers, mentioned by Hanotiaux and Heck (19 7 3) have indeed shown that in the case of soils, the various mineral forms played a part at the level of the phosphate nutrition of crops. This has also been proved by experiments

103-

in vegetation vases (Heck and Hanotiaux, 1974; 1976) which have shown as well that vegetable species could manifest preferential behaviour in relation to certain forms of this element; for instance, beetroot and lucerne in relation to P related to Ca, cereal plants in relation to P related to Al and to Fe. These last experiments have also enabled us to show that the participation of all the mineral fractions in the mineral nutrition could vary from 3 to 6% of total mineral P, depending upon the vegetable species envisaged (IRSIA, 1977-1979) . These observations applied to the sludge give an indication that the availability of mineral P in the sludge is far more important than that essentially limited to the soluble and exchangeable fractions (fr. 0 ) , even more so as the fraction of P related to Al (fr. A) is the most abundantly represented within total P of the sludge, and there it is a question of a fraction which has, as a rule, proved to be more easily assimilated by crops than the others. Fraction C (P related to Ca) which is fairly well represented within total P, takes on a special importance if one considers the preferential behaviour of beetroot and lucerne in respect to this form of P. It should be noted that this fraction is more important in the works where the sludge shows a high degree of CaO (Fleurus: 8 7 83 mg of CaO/100 g dry matter; Rhines: 12 018 mg CaO/100 g dry matter; these figures should be compared with the works at Saive, 4 2 62 and the one at Bastogne, 4 348 (Groupe d'Etude pour 1'Utilisation des Boues, 1977-1978)). Fraction B (P related to Fe) is a fraction especially accessible to cereal plants. Among all the fractions, it is the one which presents the greatest variability over a period of time. Moreover, in certain centres, it can be virtually nonexistent or very scantily represented. One can conclude from these various considerations that it is difficult to specify the availability of mineral P in the sludge. Indeed, one can expect this availability to vary in function of the sludge and of the vegetable species one intends

to cultivate. It should be added to these factors, the interaction of the various forms of P in the sludge with the soil constituents. In an initial approach, one can estimate the participation of mineral P in the sludge by counting on the participation of the fraction 0 and of all the other three fractions to the amount of 3 to 6% of their sum. As far as the organic fraction is concerned, its participation will all depend on the mineralisation of the organic matter. If one accepts the same degree of mineralisation as that recognised for organic N of the sludge ( 20%)(Groupe d'Etude pour l'Utilisation des Boues, 1977-1978), this organic fraction of P, allowing for its importance (15 to 35% of total P ) , can constitute a significant contribution. The sum of these various participations leads to a potential utilisation of P in the sludge which can be important, as shown in the following example based on the average values: for instance, the sludge at Fleurus at 5.5% dry matter (Groupe d'Etude pour l'Utilisation des Boues, 1977-1978), the phosphate spectrum of which is given in Table 1, and spread to the amount 3 of 100 m /ha that is 5 500 kg of dry matter/ha, or again, 335 kg of P 2 0 /ha distributed as follows: Fr. 0 50 Fr. A 134 Fr. B 12 Fr. C 89 Org. P 50

contribution by Fr. 0 =50 contribution by Fr. A, B, C : 3% to 6% of (134 + 12 + 89) = 7 to 14 contribution by org. P :20% of 50 = 10

which comes to a total of from 67 to 74 kg P20c or an average of 70 kg, or else 21% of total P spread.

105-

CONCLUSION From the analyses carried out on total P, the sludge from the industrial and urban wastewater purification plants has proved to be material rich in P with the restriction, however, that there exists a very great variability over a period of time of the contents observed from the same source and that this variability also occurs between the sources. As far as the different forms of mineral P present are concerned, the fraction which is best represented is fraction A and the one showing the lowest values is fraction B. The fractions 0 and C are moderately represented. The organic fraction is important and can represent up to 1/3 of total P. The accessibility of these different fractions is questionable, but a calculation by default enables one to consider the participation in the mineral nutrition of plants of at least 20% of total P of the sludge.

-106-

REFERENCES Comite pour 1'Etude de la Fertilite Chimique du Sol (IRSIA), Rapport d'Activites 1977-1979. Service de la Science du Sol - Faculte des Sciences Agronomiques de l'Etat, Gembloux. Groupe d'Etude pour l'Utilisation des Boues, Rapport d'Activites 1977 - 1978, lire partie, Faculte des Sciences Agronomiques de l'Etat, Gembloux. Chang, S.C. and Jackson, M.L., 1957. Sci., 83_, 113-144. Hanotiaux, G., 1964. Critique. 190. Le Fractionnement des formes du P du sol. Etude Les recherches scientifiques en agriculture. Tome I: 173Agressivite des especes vegetales Fractionation of soil phosphorus. Soil

Ministere Agr. Brussels.

Hanotiaux, G. and Heck, J.-P., 1973.

vis-a-vis des formes du P sol. I. Definition du probleme, Pedologie, XXIII, 1, p. 27-38. Heck, J.-P. and Hanotiaux, G., 1974. specifique par les plantes. Le P du sol et son utilisation Transactions of the 10th Int. Cong, of Le P mineral du sol et son utilisation Comptes rendus du

Soil Science, Vol. XII, 161-167, Moscow. Heck, J.-P. and Hanotiaux, G., 1976. specifique par quelques plantes de grande culture. Plantes Cultivees, Vol. I, Gent. Heck, J.-P, Barthelemy, J.-P. and Rocher, M., 1978. Caracterisation de Annales de

4e Colloque International sur le Controle de 1'Alimentation des

certains elements biogenes majeurs et metaux lourds. Gembloux, 84, 77-92.

- 107-

DISCUSSION H. Kuntze (FRG) People who have used the Chang and Jackson method for soil analytical purposes know that the limits between the fractions are not clearly defined. A modified version of this method has been made by Fink and Scharafat in our country combining, for example, fractions A and B. What is your experience on this point? Secondly, I think we should compare the results of your sewage sludge analyses with similar experiments on soil phosphorus fractionations. Do you have any material for comparing the different phosphoric fractions in the sewage sludge with those fractions in the soil?
M. Rocher (Belgium)

The method we used is not exactly the Chang and Jackson method. It was modified by Hanotiaux to try to give a good repetition in fraction A and fraction B. The details can be found in Hanotiaux (1964) which is listed in the bibliography to my paper. We have made some comparisons with soils.

- 108-

PHOSPHORUS IN SEWAGE SLUDGE IN FINLAND I. Koskela Agricultural Research Centre, Finland. 1. INTRODUCTION The need for phosphorus removal from sewage sludge became obvious in Finland during the 19 60's. Chemical phosphorus removal was introduced to supplement the traditional mechanical biological sewage treatment at the beginning of the 1970's. In Finland ferrous sulphate is the most widely used chemical for this purpose. 2. SIMULTANEOUS PRECIPITATION OF PHOSPHORUS In Finland simultaneous precipitation of sewage is widely practiced by adding FeSO^VH^O in liquid form (saturated solution) to the influent of a biological sewage treatment plant, pretreatment processes or aeration basin. It is dosed continuously or proportionately to the influent flow. This is the case at moderate or bigsize treatment plants. At small or extended aeration plants ferrous sulphate is usually dosed in crystalline form a few times a day in the aeration basin. The molar ratio of ferrous sulphate and total phosphorus should be in excess of 1.5 in order to reach the expected average level of phosphorus removal (> 80%'or effluent < 1.5 mg Ptot/D F o r a n average influent of 10 mg P/l this would mean a dose of 135 g ferrous sulphate to a m of sewage. In practice normal dosages of ferrous sulphate are 100 to 150 g/m sewage. The total concentration of iron in the influent as well as effluent of simultaneous precipitation is usually 1 to 2 mg Fetot/1 Resulting average concentrations in sludge dry solids, depending on the quality of sewage, effective ness of sewage treatment and sludge treatment method, are
109

2.0 to 3.7% for P t o t and 10 to 15% for F e t o t . The phosphorus content of this sludge is more than twice as high as that of conventional biological sludges. The iron content of conventional biological sludges is about 2%. In theory, sludge quantities are expected to increase by 25%. In practice, however, an increase has often not taken place due to the improving settling characteristics of sludge which have led to longer sludge age and higher destruction of sludge organic matter. One would usually expect the sludge quantity to increase by 10 to 15%. At the beginning of 1979, of the total number of 559 municipal sewage treatment plants serving more than 200 inhabitants, 341 were simultaneous precipitation plants. These treated 35% of the total sewage flow. This figure is expected to increase in the near future. It must be emphasised that the quoted figures of phosphorus removal effect are averages covering all plants, even those which are poorly operated. A well operated plant can be expected to produce an effluent quality of less than 0.7
m

<3 Ptot/1-

3. SIMULTANEOUS PRECIPITATION IN CITY OF HELSINKI Ferrous sulphate is added at the beginning of the purification process, oxidised in the aeration basin and removed together with the surplus sludge. In the City of Helsinki chemical surplus and primary sludges are then digested in the normal way, conditioned with polymers and dewatered in centrifuges. The City of Helsinki, 500 000 person equivalent, produces about 12 000 tons of digested sludge per annum (dry basis). About 15% of this is utilised by farmers, 50% on lawns and road banks or is composted, and the remaining 35% is disposed on municipal dumps. No sludge is incinerated.

no-

In 1979 total P-content of influent was 5.8 to 9.3 mg/1 and that of effluent 0.8 to 1.0 mg/1. Ferrous sulphate was used 70 to 110 g to a m of sewage. P-content of sewage sludge was 3.4 to 4.7% in dry matter and Fe-content 4.4 to 9.5%, dry matter content 18 to 25%. 4. EXPERIMENTS AT THE AGRICULTURAL RESEARCH CENTRE FeSO.-sewage sludge contains quite a large amount of phosphorus, and this is sometimes greater than nitrogen content. It is not clear, to what extent this can be used by plants. At the Agricultural Research Centre a pot experiment was started in 1974 to examine this problem. The experiment ran from 1974 1977. Six different kinds of soils were used (51 Mitscherlichpot) . Pot Experiment P l a n t : Lolium multiflorum
Soil No. 1 2 3 4 5 6 fine sand fine sand heavy clay gyttja clay sandy clay sphagnum peat

Italian

ryegrass
mg/1 soi.1

Humus

%
2.30 6.62 3.74 12.67 7.89

pH 5.30 6.32 6.70 4.68 5.75 3.49

P 10.5 8.3 11.0 9.5 5.0 3.2

K 105 120 300 158 299 40

Ca 50 1 580 3 200 260 2 350 200

Mg 21 100 265 69 546 40

Treatments: Every year First year only (sludge and Ci

Mn Mo B Zn

a b C

N N

2P2K2Cao-l 5 ^ 1 + Cu 2 P 2 K C a n - 1 5 Mg l + N 2 - K2Ca Mg +

" -

+ 0.5 kg Fe-sludge + 0.5 kg Fe-sludge

Ill

2 OOO mg/pot N (NH N04> 400 mg/pot P (Ca(H2P04> .H20)

K ^2 = 2 000 mg/pot K (KC1) Ca . - 12 OOO mg/pot CaCO-, Mg = 200 m g / p o t Mg (MgSo..7H O) F e - s l u d g e ~ 20% d r y m a t t e r Repeats: 3

5.

RESULTS

Best y i e l d r e s u l t s were reported for the a p p l i c a t i o n of sewage sludge t o clay s o i l s (Table 1 ) .

TABLE 1 TOTAL YIELDS g/POT (DRY MATTER IN THE YEARS 1974-1977 Treatments Chemical Chemical + Sludge Chemical without P + sludge 137.6 155.8 202.5 178.0 214.4 174.2

Soil

1 2 3 4 5 6

fine sand fine sand heavy clay gyttja clay sandy clay sphagnum peat

168.1 166.1 180.6 173.9 196.3 161.5

161.5 181.4 212.6 191.9 226.6 171.7

Years, soils and treatments each had significant effects at 99.9% level on the yields. Sludge had a positive effect on the phosphorus content of ryegrass. The highest P-contents without sludge were found in plants which were grown in sphagnum peat (= organic matter). No negative effects on crop yields were reported from the application of sewage sludge containing large amounts of ferrous sulphate. Similar results were obtained from field experiments (Tables 2 to 4).
112-

TABLE 2 YIELDS g/POT DM

Soil

Treatments P Chem. sludge I II

1974 Yields III IV Total I II

1975 Yields III IV Total

a b c a b c a b c a b c a b c a b c

+ +

+ +

+ +

10.60 15.57 12.33 17.03 18.60 13.70 19.47 18.90 18.77 12.60 18.63 15.73 14.77 19.87 19.40 16.20 19.50 20.40

9.40 13.97 10.97 16.40 19.20 18.20 17.30 17.80 19.57 14.87 18.87 18.50 16.47 20.40 20.93 1 9 . OO 16.80 19.70

25.63 15.17 24.90 18.47 13.80 17.57 8.27 16.80 14.30 21.47 17.83 22.50 19.67 21.37 22.87 6.00 8.40 11.40

10.23 7.77 10.40 9.47 11.23 12.77 3.96 13.20 12.40 17.17 12.47 17.10 11.13 19.53 18.87 2.70 6.90 7.20

55.86 52.48 58.60 61.37 62.83 62.24 4 9 . OO 66.70 65.04 66.11 67.80 73.83 62.04 81.17 82.07 43.90 51.60 58.70

6.90 11.67 3.00 9.07 11.33 5.00 19.00 18.67 17.67 8.70 16.10 8.30 21.30 22.23 20.03 21.00 23.10 19.80

7.13 10.37 3.87 8.07 7.73 6.07 10.10 10.67 10.73 6.60 8.87 6.57 9.77 10.40 10.07 9.00 9.20 9.10

16.40 17.10 10.50 17.20 14.27 20.63 9.93 16.70 16.60 18.20 17.37 18.50 10.33 14.80 15.20 5.80 6.90 10.00

12.70 9.10 26.83 6.00 15.90 10.07 4.50 7.97 6.87 7.40 9.00 10.27 4.97 9.50 9.27 3.00 4.30 4.90

43.13 48.24 44.20 40.34 49.23 41.77 43.53 54.01 51.87 40.90 51.34 43.64 46.37 56.93 54.57 38.80 43.50 43.80

+ +

+ +

+ +

+ +

+ +

+ +

+ +

+
+

+ +

+ = phosphorus in chemicals or sludge

Table 2 (Continued)

TABLE 2 (Continued)

Soil

Treatments P Chem. Sludge I 8.47 4.50 1.10 8.73 9.83 5.30 20.53 21.90 19.97 7.70 14.60 2.47 23.2o 20.30 15.67 24.90 18.80 22.40 II 12.43 8.07 1.20 12.93 19.90 10.23 17.37 16.87 13.43 17.70 18.77 7.83 15.03 15.97 16.63 8.20 10.40 9.00

1976 Yields III 12.90 14.17 2.07 11.23 8.33 12.93 8.00 8.97 9.90 lO.OO 7.50 19.33 6.70 10.17 12.33 3.40 4.70 4.00 IV 8.80 8.43 12.03 2.83 2.50 3.27 2.47 2.73 3.13 3.00 2.87 5.30 2.30 3.17 3.93 1.50 2.20 2.20 Total 42.60 35.17 16.40 35.72 40.56 31.73 48.37 50.47 46.43 38.40 43.74 34.93 47.23 49.61 48.56 38.00 36.10 37.60 I II 8.80 8.97 2.00 18.30 17.93 4.17 13.07 13.07 12.20 7.83 10.60 7.33 9.87 9.33 7.67 9.4 9.8 10.3

1977 Yields III 12.03 11.97 5.93 8.17 8.53 12.73 10.07 9.87 13.OO 13.07 6.00 12.30 14.77 lO.OO 1.27 4.9 5.4 5.1 IV 5.63 4.70 10.43 2.17 2.27 3.17 2.83 2.73 3.57 3.17 2.27 2.97 4.10 2.87 3.60 1.5 1.6 1.7 Total 26.46 25.64 18.36 28.64 28.73 20.07 39.74 41.40 39.14 28.47 29. lO 25.63 40.61 38.90 29.21 40.80 40.50 34.10

19741977

a b c a b c a b c a b c a b c a b c

+ +

+ +

+ +

+ +

+ +

_ 13.77 15.73 10.37 4.40 10.23 3.03 11.87 16.70 6.67 25.0 23.7 17.0

168.05 161.53 137.56 166.07 181.35 155.81 180.64 212.58 202.48 173.88 191.98 178.03 196.25 226.61 214.41 161.50 171.70 174.2o

+ +

+ +

+ +

+ + +

+ +

+ +

+ = phosphorus in chemicals or sludge

TABLE 3 P o/ 00 Soil Treatments P Chem. a b c a b c a b c a b c a b c a b c + + + + Sludge I 1.74 2.54 2.24 1.98 2.93 2.75 3.90 5.20 4.54 1.96 2.89 2.41 3.76 4.91 4.46 6.55 6.51 4.31 1974 Yields II 3.19 4.62 4.21 2.68 4.92 4.09 4.95 6.49 5.46 3.26 4.82 3.75 3.38 5.68 5.00 6.56 8.55 6.00 III 1.93 3.59 2.80 2.47 5.69 4.29 4.93 5.39 5.28 2.72 4.37 3.49 4.65 6.70 6.54 5.69 8.30 6.72 IV 2.34 3.57 3.51 2.56 4.65 4.21 3.62 4.38 4.26 3.74 5.42 4.51 3.37 3.86 3.71 5.07 7.45 5.91
I

1975 Yields II 1.80 1.86 1.29 2.80 3.23 2.64 4.02 4.72 3.78 3.22 3.94 2.81 4.00 4.75 3.52 5.69 6.76 3.92 III 1.99 2.65 1.94 2.91 4.15 3.58 4.60 5.56 4.61 4.51 4.74 4.21 4.11 5.23 4.84 9.46 8.87 5.60 IV 1.72 3.19 1.59 4.03 4.02 3.77 2.80 3.71 3.88 4.79 4.42 3.81 2.51 3.35 3.55 8.08 6.41 5.99

_
+ +

+ + + + + +

1.49 1.96 1.34 2.01 2.46 1.95 2.83 3.71 3.04 2.13 2.45 1.84 2.33 2.81 2.37 5.34 5.48 4.31

+ +

+ +

+ +

+ +

+ +

+ +

+ = phosphorus in chemicals or sludge

Table 3 (Continued)

TABLE 3 (Continued)

Treatments Soil P Chem. 1 a b c a b c a b c a b c a b c a b c + + Sludge I 2.11 2.39 II

1976 Yields III 2.09 3.11 IV 2.33 4.67 1.47 4.82 6.26 3.83 4.51 4.67 4.58 5.10 6.29 4.55 4.78 4.57 4.90 10.92 10.56 6.65 I

1977 Yields II 2.05 2.92 III 2.81 3.68 IV 2.37 3.85 1.02 3.66 4.08 2.43 2.84 3.08 2.74 3.12 3.98 2.70 2.87 4.05 2.97 7.64 6.77 3.88

+ +

+ +

+ +

+ +

3.00 1.94

3.49 4.17 2.76 4.90 4.95 3.80 3.84 3.77 3.14 4.87 5.50 4.55 11.59 7.10 6.21

_ 3.24 3.26 2.80

2.84 3.35 3.08 3.83 2.66 2.85 3.18 2.24 3.13 4.24 2.38 5.72 5.25 2.89

+ +

+ +

4.71 4.59 3.79 4.01 4.05

+ +

+ +

3.23 5.21 3.84 5.93 5.99 5.16

_ 3.20 3.42 2.76 3.76 3.83 2.26

+ +

+ +

+ +

phosphorus in chemicals or sludge

TABLE 4 Fe ppm Treatments Soil Chem. 1 a b c a b c a b c a b c a b c a b c + + + + P Sludge I 185 172 181 194 197 186 225 207 256 190 155 148 314 214 232 114 117 164 1974 Yields II 217 237 166 188 175 224 208 258 268 232 268 276 III 165 162 136 139 124 151 229 179 224 176 160 168 IV 162 151 150 165 201 158 234 262 333 315 244 263 229 185 168 156 157 152 I 153 152 158 147 152 146 186 172 166 148 145 183 286 154 154 138 146 177 1975 Yields II III IV 105 108 99 118 119 130 251 173 150 130 156 120 208 149 154 133 132 134 I 124 139 1976 Yields II 202 109 III 82 90 IV 105 105 118 75 81 74 139 134 123 84 102 . 87 142 111 112 99 92 105 I 1977 Yields II 117 118 III 113 106 IV 106 76 94 89 89 103 194 150 125 94 117 89 102 135 92 77 81 69

_
+ +

131 128 130 117 121 149 143 112 108 151 185 165 153 125 176 108 113 120 178 176 158 119 106 116

_
+ +

118 110 122 101 201 161 106 86 132 105 103 98 83 82 88

162 178 143

110 117

+ + + +

+ +

+ + + +

135 136 133 132 128

127 159 141 106 86 99 134 112 127 106 111 96

+ +

122 121 130 92 83 87

+ +

289 193 259 167 311 153 181 207 184 137 142 163

150 153 123 119 151 159 115 127 155 86 85 108

138 129 129 113 123 128

+ +

+ = phosphorus in chemicals or sludge

REFERENCES Koskela, I. , 1978. Puolanne, J., 1980. Viitasalo, I., 1979. Disposal of municipal sludges containing heavy metals Seminar on Heavy Metals. Copenhagen 4-7 June 1978. Personal communication. National Board of Waters,

in agriculture.

Helsinki, Finland. Cadmium, copper, zinc, manganese and iron accumulation in cereal seeds during iron-containing sewage sludge fertilisation. Management and Control of Heavy Metals in the Environment, imperial College, London, 18-21 September 1979.

DISCUSSION

S. de Haan

(Netherlands)

Do you agree that the bad effect of phosphorus on the light sandy soil was due to phosphate fixation? Looking at your Tables 1 and 2 this seems to me to be the case.
I. Koskela (Finland)

I think you are right.

- 118

INFLUENCE OF NUTRITIONAL AND PHYSIOLOGICAL FACTORS ON PHOSPHORUS CONTENT OF ANIMAL MANURES P.CM. Simons1 and A.W. Jongbloed2 'Spelderholt Institute for Poultry Research, Beekbergen, Netherlands.
2

Institute for Livestock Feeding and Nutrition Research "Hoorn", Lelystad, Netherlands.

ABSTRACT There are several influence and calcium requirements nutritional of livestock and physiological disposed are under health factors The that phosphorus

the amount of phosphorus

of in manures. discussion. and genetic of

Production, been enumerated.

age, sex, environment, In the period 1973/1974 with decreased

factors

have levels further.

- 1976/1977 should

the phosphorus even

in the animal mixed feeds in the compound feeds

10%. The levels

phosphorus

in the Netherlands

be decreased

-119-

All animals require feed for their body maintenance, reproduction and growth. In the Netherlands, practically all the feed for pigs and poultry and about 50% of cattle feed is produced by the feed industry. The main component of poultry feed is maize, although other cereals like wheat and sorghum are also used. Several plant by-products, for instance soyabean oil meal, wheat bran and animal residues (meat and bone meal) are included in the diet. On average, pig feeds contain about 20% cereals and a lot of by-products like maize gluten meal, wheat bran and soyabean oil meal. During recent years, tapioca has often also been used in diets for poultry and pigs. Cattle consume compound supplements as well as grass products (grass, hay and silage) and maize silage. These supplements are produced and supplied by the feed industry and are almost entirely composed of byproducts. Table 1 gives an idea of the use of commercial mixed feeds for livestock in the Netherlands.
TABLE 1 CONSUMPTION OF COMMERCIAL MIXED FEEDS IN THE NETHERLANDS (TONNE S/YEAR;

1978/1979)
Cattle Pigs

4 684 047 5 968 078 1 665 611 1 024 579

Poultry (layers) Poultry (broilers)

Almost all the ingredients of the commercial mixed feeds are imported, so all farm animals can be kept on a small surface area in the Netherlands. For optimum performance and health of the animals, their feeds must contain a certain amount of energy, protein and several minerals and vitamins. Of the minerals, phosphorus is
- 120-

of critical importance for the development and maintenance of the skeleton. It is also a major component of cell membranes, milk and eggs, and is essential for several anabolic and catabolic reactions. About 75 - 80% of the phosphorus in the body is found in the skeleton. Slaughter pigs of 110 kg contain about 550 g phosphorus, and a fowl of 1.5 kg, about 8.25 g. Before discussing the factors which influence the excretion of phosphorus, let us present a simple model of the phosphorus metabolism in the animal (Figure 1 ) . FACTORS IN EXCRETION OF PHOSPHORUS There is a large individual variation in excretion of phosphorus between animals caused by genetic factors, health and environmental conditions. Digestive disturbances particularly, increase faecal excretion of minerals by decreasing their absorption in the intestines. Furthermore, excretion of phosphorus can be influenced by 1) nutritional factors and 2) physiological factors. 1. Nutritional factors (a) Phosphorus in the diet When phosphorus levels above the minimum requirement are provided, excretion of phosphorus increases about linearly with the intake of phosphorus. Only a small amount of the extra supply of phosphorus will be deposited in the bones. In Figure 2 the relationship is given between intake and excretion of phosphorus in pigs and in poultry. The absorption of phosphorus in the intestine is partly by diffusion and partly by active transport. Absorption of phosphorus increases linearly with the intake of phosphorus. If more phosphorus is absorbed, more will be excreted in the urine (also a linear relationship).
-121-

FEED

SOFT TISSUES

DIGESTIVE JUICE <

ABSORPTION

URINE FAECES

Fig. 1.

EXCRETION MG P PER DAY

2100 -,

1900 1700

1500 -

1300 -

1100

900 -

700 500
CONTENT OF P 1 1 1 1 1 1 (%) 1

0.20
=

0.40

0.60

0.80
1 1 0 KG

1.00

1.20 .

1.40

PIGS FROM 2 0 -

= LAYING HENS Fig. 2. R e l a t i o n s h i p between c o n t e n t of P i n d r y m a t t e r of t h e d i e t r a t e of e x c r e t i o n of P . 123and

(b) Calcium in the diet For absorption of calcium in the intestines, no phosphorus is required and for the absorption of phosphorus no calcium is required. Calcium and phosphorus are the main mineral constituents of bone. In skeletal bone, calcium and phosphorus are laid down as hydroxyapatite Ca1 10 (P0 4 ) 6 (OH) 2 . This means that calcium and phosphorus are deposited in bone in a narrowly defined ratio. Also in the whole body (with the exception of the young animal) this ratio is between narrow limits (for instance, 1.5 to 1.7 in pigs). Therefore a low content of calcium and a high content of phosphorus result in a high excretion of phosphorus in urine. A high content of calcium, on the other hand, can lead to the formation of insoluble calcium salts (such as calcium phytate) and decreased phosphorus absorption. Therefore in formulating feed for livestock (except laying hens), it is necessary to devote some attention to the optimum ratio of calcium to phosphorus in the diet. Laying hens produce a lot of egg shell material containing mainly calcium carbonate and hardly any phosphorus. There is a lot of discussion about the ideal value of Ca/P ratio, because the availability of phosphorus is different in the different sources and is influenced by several other factors, like age and feed composition. (c) Source of phosphorus Feedstuffs of plant origin contain a certain amount of phosphorus which is gradually utilised during germination of the grain. This phosphorus consists of an inorganic and an organic part. The major part, however, about 60 - 75%, consists of phytic acid or phytate, together sometimes called phytin. Phytin consists of inositol with six phosphorus acid

124-

groups. Tubers, roots, leaves and stalks contain very little phytin, if any, as it is mostly found in cereal grains or other seeds; the amount present being highest when the seed is ripe. Phytin phosphorus is used in germination of the seed and is hydrolised by acid or by an enzyme called phytase. Monogastric animals are considered by many scientists to be unable to utilise much phytate, because of lack of the enzyme phytase in the digestive tract, whereas the phosphorus of phytate is available to ruminants because of large amounts of phytase produced by the rumen microflora. There is some doubt about the utilisation of phytin phosphorus in the digestive tract. Estimates of 0 - 40% have been made. In very young animals, the utilisation of phytin is worse than in older ones. Also an increase of calcium in the diet has an unfavourable influence on the utilisation of phytin phosphorus by the formation of insoluble calcium phytate. In most raw materials of feed, the amount of phosphorus is too low for optimum production and health, so that extra inorganic phosphorus has to be supplied. In the different sources of inorganic phosphorus, phosphorus can be bound in a different chemical form and the solubility and absorption in the digestive tract may vary. The lower the absorption, the more will be excreted in the faeces. (d) Vitamin D Metabolites of vitamin D are formed in the liver and kidneys. They play an important role in calcium and phosphorus absorption as well as bone mineralisation. Vitamin D deficiency, therefore, causes an increase in phosphorus excretion. Normally vitamin D in animal diets is added to an adequate level. However, some animals have a genetic variation in their vitamin D metabolism, which results in greater excretion of phosphorus.
- 125-

(e) Metabolisable energy When the content of metabolisable energy in the diet is increased, the level of protein, vitamins and minerals have also to be increased. Thus a diet with a higher percentage of total phosphorus will result in a relatively lower level of phytin phosphorus and more available phosphorus. This can lead to a higher utilisation of phosphorus, which in turn reduces excretion. 2.' Physiological factors (a) Age in association with bodyweight The need for phosphorus at a younger age is larger than at an older one and the utilisation of phytin phosphorus is lower at a younger age. In the Netherlands one diet with the same dietary constituents is often supplied for practical reasons for pigs from 30 - 110 kg and one diet for broilers from one day till 6 weeks of age. As the need for phosphorus at a younger age is largest and as the level of phosphorus in the feed is determined by the need of the younger age, there is a surfeit of phosphorus at the older age. There is a linear relationship between retention (intake minus faecal and urinary losses) of phosphorus as a percentage of the intake and bodyweight (Figure 3 ) . A way of reducing the excretion of phosphorus lies in the production of a wider range of feeds in the growing period; for instance, for slaughter pigs one diet from 30 to about 60 kg bodyweight and one diet with a lower phosphorus level from 60 to 110 kg. For broilers, possibly one diet for the first three weeks and another with a lower phosphorus level in the last three weeks. (b) Production An important factor in the amount of phosphorus excretion is the form of production (eggs, milk or growth).

- 126-

P-RETENTION %

50-

40-

30-

T"

50

70

90

100 BODYWEIGHT (KG)

Fig. 3.

Influence of body weight on p r o p o r t i o n of P r e t a i n e d from a d i e t with content of 0.55% P i n dry m a t t e r .

Eggs and milk require some phosphorus which has to be supplied to the feed. Calcium deposition, especially in layers, is also an important factor. On practical diets with much limestone for laying hens, bone resorption takes place when the egg shell is formed. This is attended with extra phosphorus excretion. For meat production, animals with a high growth rate need more phosphorus than animals with low growth rate, because meat contains much protein having quite a lot of phosphorus. During the last decade, especially for pigs, selection has led to animals with more protein deposition, which results in a higher requirement for phosphorus (Gunther and Rosin, 1970). For fat production, in practice, no extra phosphorus is required. (c) Sex In general, male animals have more bone than females, when compared at the same bodyweight. When supplied with diets of the same composition, male animals therefore excrete less phosphorus than females, but the difference is small. Having reviewed the nutritional and physiological factors in the excretion of phosphorus, let us review our estimates of excretion of phosphorus in livestock in the Netherlands. For calculation, normal dietary conditions, average production and feed conversion ratios are assumed. The levels of phosphorus in the different feeds were measured by the TNO Working Group on Minerals in Feedstuffs in relation to Manuring and Environment. For 1976/1977 the following values have been found. Requirements are given on the right.

128-

TABLE 2 Content of phosphorus in dry matter of feeds in 1976/1977

( % )

Content of phosphorus recommended

( % )

Cattle Pigs Laying hens Broilers

0.60 O.IO 0.75 0.08 0.83 0.10 0.80 0.07

0.50 0.55 - 0.60 0.65 0.65 - 0.80

In 1974, Kemp calculated how much phosphorus was excreted by cattle, pigs and poultry on diets with different levels of phosphorus. The excretion (faeces and urine) as a percentage of intake for the diet levels mentioned above is shown in Table 3.
TABLE 3 Proportion of phosphorus excreted ( % ) Cattle Pigs Laying hens Broilers 70 77 91 61

The Dutch Commodity Board for Animal Nutrition has published the total feed consumption for the different animals and the TNO Working Group has calculated excretion of phosphorus on the basis of the percentages excreted as given.

129-

TABLE 4 INTAKE AND EXCRETION OF PHOSPHORUS BY DIFFERENT ANIMALS I N TONNES PER YEAR (1976/1977)

Intake of phosphorus Cattle Pigs Poultry 24 610 33 232 17 116 74 958

Excretion of phosphorus 16 508 26 254 13 179 55 941

Excretion of phosphorus by the different animals was also estimated in 1972/1973 and in 1978/1979, as shown in Table 5.
TABLE 5 EXCRETION OF PHOSPHORUS BY DIFFERENT ANIMALS IN 1972/1973, 1976/1977 AND 1978/1979 (TONNES)

Excretion of phosphorus 1978/1979 Cattle Pigs Poultry 17 352 27 467 14 358 59 177

Excretion of phosphorus 1976/1977 16 508 26 254 13 179 55 941

Excretion of phosphorus 1972/1973 13 682 25 923 13 513 53 118

The increase in phosphorus excretion (about 5%) from 1972/1973 to 1976/1977 is attributable mainly to dairy cows. The use of commercial compound feeds for cattle increased by 40% and the phosphorus level in those compound feeds decreased from 0.70% to 0.60%. From 1976/1977 till 1978/1979 the phosphorus excretion again probably increased by 5% for each category of livestock, because of an increase in the number of stock in the country.
- 130-

Of the total phosphorus excreted by livestock, about 30% comes from cattle, 50% from pigs and 20% from poultry. It is estimated that from commercial compound feeds for cattle, pigs and poultry, the amount of phosphorus coming into the soil in 1976/1977 in the Netherlands was 29 kg/ha (for P-O- 66 kg/ha). The amount of phosphorus from fodder produced on the farm is not included in this value. The distribution of excreted phosphorus over the whole country is very variable. In the Provinces Gelderland, North Brabant and Limburg, where livestock are kept intensively, it is about twice the average. Groningen, North Holland and Zeeland with a lot of arable land are least affected by this manure phosphorus. For the distribution of phosphorus over the whole country, the manure banks (responsible for disposing of manure from some provinces) could now play a very important role.
REFERENCES Gunther, K. and Rosin, G., 1970. Ueber die Ansatzkapacitat des FleischZ. Tierphysiol.

schweines fur Mineralstoffe im Verlauf des Wachstums. Tierernahr. Futtermittelk. 26: 179-195. Kemp, A., 1974.

Fosfaatuitscheiding in mest en urine bij landbouwhuisdieren Landbouwk. Tijdschr.

in relatie met de fosfaatopname uit net voer. 86: 114-119.

Working Group on Minerals in Feedstuffs in relation to Manuring and Environment, 1975. Enkele minerale bestanddelen van mengvoeders

in relatie tot de behoefte van de dieren, de uitscheiding in de mest en urine alsmede enkele gevolgen voor bodem, plant en dier. Working Group on Minerals in Feedstuffs in relation to Manuring and Environment, 1979. De gehalten van mengvoeders aan enkele minerale bestanddelen met betrekking tot de behoefte van de dieren, de uitscheiding in de mest en urine, alsmede enkele gevolgen voor bodem, plant en dier.

131-

DISCUSSION A.E. Johnston (UK) In your Table 4 you give excretion of phosphorus which is obviously the total of faeces and urine. Approximately what proportion is in faeces and what proportion in urine?
P . C M . Simons (Netherlands)

It is about half in each.

H . Tunney (Ireland)

I think it might well be half in faeces and half in urine in pigs but in cattle it would be mostly in the faeces and very little in the urine. P.CM. Simons In poultry, however, it is mostly in the urine. R. Unwin (UK) Can you confirm that the figure of 29 kg/ha of P is average figure for the whole country and can you give an cation of what extra phosphorus is being excreted by the produced on the farm, which you said was not included in figure? P.CM. Simons The figure of 29 kg/ha of P is an average for the whole country. The maize which is produced on the farm goes through the animals and all the phosphorus comes on the soil there. R. Unwin Could you give us an indication of the total P loading that is going back? P .CM . Simons No, I cannot.
- 132-

an indifodders that

E.G. Coker (UK) Your Table 4 gives a phosphorus budget of 130 000 t/year. How does this compare with the amount of purchased phosphorus in mineral fertiliser? P.CM. Simons It is nearly the same amount. P. Sauerbeck (FRG) In your conclusion you say that the phosphorus content of these materials should be decreased even further. From the nutritional point of view I do not think there is much you can do about the percentages of utilisation and excretion, so how do you justify the statement that in animal feed the phosphorus content could be decreased as compared to what it contains at the moment? P.CM. Simons Of course we cannot say that this can be done for all animals. However, I am sure that in last period that broilers are fed, the phosphorus amounts are too high. This also applies with pigs in the period from 60 kg to 110 kg. It can also be a little lower in cattle feeds. For layers in our country the amounts are generally too high. But for young broilers and for young pigs you have to be careful in lowering the amounts.

- 133-

SESSION

III

PHOSPHORUS VALUE OF WASTES

Chairman: A. Dam Kofoed

- 135-

PHOSPHORUS VALUE OF SLUDGES RELATED TO THEIR METAL CONTENT B. Pommel

A g r o n o m i c S t a t i o n , INRA, R e s e a r c h C e n t r e o f B o r d e a u x , Domaine d e l a Grande F e r r a d e - 3 3140 P o n t d e l a Maye, France. ABSTRACT Two experiments sand (2 kg) and placed calcium phosphate were tested, discussed. uptake. A third ryegrass observed. efficient to 50% after experiment has been carried out with ryegrass in pots doses value placed of were rose at two zinc Sludge have been carried in a greenhouse. levels, out with maize in pots Two phosphorus sources flocculated a supply filled (monosewage of iron. Zn sludge) Yield absorption P with

and a digested,

polyelectrolyte with and without of available Zn. Fe.

and concentrations by maize and toxicity

of P, Fe and Zn in plants was a source of absorbed

were measured and are Fe decreases Zn supply decreases

Increasing

in a growth chamber. After seven

Kinetics

of absorption sources

of phosphorus at four sludge by plants;

by the tops was only this

from the same two phosphorus days of root-soil phosphate as monocalcium 75 days.

different

contact,

15% as

for P uptake

137-

1.

INTRODUCTION

The phosphorus content of sewage sludges is relatively high: among 250 samples, the median value is 2.3%(dry matter basis) and extreme limits < 0.1 to 14.3%(Sommers, 1977). However, valorisation of sewage sludge as P fertiliser requires knowledge of sludge phosphorus availability to plants. Absorption of phosphorus by plants depends on: 1. Chemical forms of phosphorus in the soil sludge system. Phosphorus will be absorbed more or less quickly and more or less completely according to the nature of these forms. For that reason a short term and a long term absorption experiment has been made with ryegrass. 2. Metallic ions present in soil solution. Indeed, some of them have antagonistic action towards phosphorus absorption by plants; this fact may explain some observations made in a field experiment by Juste and Solda (1977), who found a significantly lower phosphorus content in maize from sludge plots than from control plots. However, the sludge plots received six times as much total phosphorus as the control plots and contained three times as much citric acid extractable phosphorus. Therefore, two experiments were carried out with maize receiving sludge or monocalcium phosphate, at different Zn and Fe levels in soil (Pommel, 1979). 2. MATERIALS AND METHODS

Two experiments were carried out with maize in pots filled with sand (2 kg) and placed in a greenhouse. The waste studied is an urban, digested, polyelectrolyte flocculated sludge (Table 1 ) . There were five treatments, each one repeated five times:

138-

C, O Zn - control treatment: monocalcium phosphate is the source of phosphorus. This element is supplied at the same level as with the sludge; S, 1 Zn - sludge at a rate equivalent to 10 t/ha (dry matter basis) is the source of phosphorus; C, 1 Zn - control treatment which received zinc sulphate; this metal is supplied at the same level as with the sludge; S, 5 Zn - sludge treatment plus fourfold zinc; C, 5 Zn - control treatment plus fivefold zinc.
TABLE 1 COMPOSITION OF THE SEWAGE SLUDGE (DRY MATTER BASIS)

Ash % Carbon % Nitrogen Kjeldahl Calcium % Magnesium % Iron % Copper ppm Manganese ppm Zinc ppm Cadmium ppm Chromium ppm Nickel ppm Lead ppm

54.4 29.2

2.79 4.89

Total Phosphorus (P 2 O 5 ) %

5.4
4.73 4.72

309

9 25 3 7 056
33 74

246

1 313

The second experiment (Fe) d i f f e r s from the f i r s t (0 Fe) i n t h e f a c t t h a t every p o t received t h e same q u a n t i t y of i r o n (as i r o n sulphate) as i n a sludge r a t e . Nitrogen and potassium supply was s u f f i c i e n t for a good growth. pH d i f f e r e n c e s were
139-

corrected by calcium carbonate supply. after one month.

Maize was harvested

The third experiment was carried out with hybrid tetraploid ryegrass Sabrina in pots filled with 0.7 kg sand. According to the Stanford and Dement (19 57) method, plants are grown without added P, during which time a mat of roots develops at the bottom of the container. The exposed root mat with plants intact is then placed in contact with the soil fertiliser or soil sludge system; ryegrass is clipped seven days after transfer, and then every two weeks until substratum phosphorus is exhausted. Seven treatments, each one repeated four times, were as follows: C O - control without phosphorus; SI, S3, S9 - sludge, at a rate equivalent to 3.3 - 10 - 30 tonnes/ha (dry matter basis) is the source of phosphorus? the sludge used is the same as in the previous experiments . CI, C3, C9 - monocalcium phosphate is the source of phosphorus. This element is supplied at the same levels as with sludge. All other parameters were chosen for optimal growth. Pots were placed in a growth chamber. 3. RESULTS AND DISCUSSION

Results of experiments 1 and 2 are summarised in Tables 2 and 3. They will be discussed in relation to three aspects: - sludge phosphorus availability; - supplying and bonding of iron by sludge; - zinc availability and toxicity.

140-

TABLE 2 EXPERIMENT NO.l. YIELD AND COMPOSITION OF MAIZE GROWN ON MEDIUM WITHOUT IRON. PHOSPHORUS SOURCES: MONOCALCIUM PHOSPHATE (C), SLUDGE (S) Composi tion of maize tops (DM basis) Phosphorus (o/oo) 10.3 1.3 12.7 1.5 5.7 Iron (ppm) 59 60 43 81 51 Zinc (ppm) 53 56 670 2 160 1 750 Zn/Fe in Maize tops 0.9 0.9 15.6 26.7 34.3

Treatment

Yield (DM) g/pot

0 Fe, C, O Zn 0 Fe, S, 1 Zn 0 Fe, C, 1 Zn 0 Fe, S, 5 Zn 0 Fe, C, 5 Zn

3.4 4.5 2.3 2.6 1.0

TABLE 3 EXPERIMENT NO.2. YIELD AND COMPOSITION OF MAIZE GROWN ON MEDIUM WITH IRON. PHOSPHORUS SOURCES: MONOCALCIUM PHOSPHATE (C), SLUDGE (S) Composition of maize tops (DM basis) Phosphorus (o/0o) 1.5 1.3 1.4 1.3 1.6 Iron (ppm) 91 66 109 83 135 Zinc(ppm) 34 74 316 1 416 2 236 Zn/Fe in Maize tops 0.4 1.1 2.9 17.1 16.6

Treatment

Yield (DM) g/pot

Fe, C, 0 Zn Fe, S, 1 Zn Fe, C, 1 Zn Fe, S, 5 Zn Fe, C, 5 Zn

5.0 4.2 4.9 3.7 3.5

141

3.1. Sludge phosphorus availability Phosphorus uptake by the tops of plants in treatment Fe, 1 Zn was only 70% of treatment Fe, C, 0 Zn; this difference is highly significant (more than 1 'oo); it depends on different availability of phosphorus forms, but also on zinc content of sludges that limit phosphorus absorption by the plant. In all cases, increasing zinc supply decreased phosphorus uptake; for example, phosphorus uptake by the control treatments that received zinc at the level supplied by sludge (i.e. Fe, C, Zn), was 91% of the control plots without Zn added (Fe, C, 0 Zn) . One might suppose that nickel, iron and cadmium have a similar antagonistic effect to phosphorus absorption by plants that accumulates from zinc. 3.2. Supplying and bonding of iron by sludge During the first experiment without iron supply, control plants had a very chlorotic aspect, growth was very poor and phosphorus content was very high; in contrast, plants from sludge treatments had a normal aspect and a significantly (1 /oo) higher dry matter content. Thus, sludge supply had an antichlorotic role, as iron sulphate in the second experiment: sludge contains available iron. However, in some way sludges bond iron supplied as iron sulphate: plants from sludge treatments had a lower iron content (significance: 1 /oo) than control ones, though they received twice as much total iron; soluble iron may be chelated by sludge organic matter. 3.3. Zinc availability and toxicity During the second experiment with iron content of plants from sludge treatments was (significance: 1 /oo) than from the control from sludge is not as available as zinc from supply, zinc much lower treatment: zinc zinc sulphate.

When zinc supply increases, zinc absorbed increases very much and iron absorbed increases a little; absorption of iron may, in some way, protect plants against zinc toxicity. Maizes
-'142 -

from Fe, C, 1 Zn treatments that received iron were less affected by zinc toxicity than plants from 0 Fe, C, 1 Zn treatments, having a lower zinc content, higher iron content and yields nearer to the control without zinc. Takkar and Mann (1978) observed that maize yield begins to to decrease with zinc concentration in the tissue above 100 ppm; it is divided by three with a concentration of 300 ppm, whilst above 600 ppm signs of toxicity appear. Here, with a great deal of available iron present in the soil (experiment 2 ) , concentrations of 316 ppm zinc in maize tissues (Fe, C, 1 Zn treatments) did not affect yield; with more than 2 000 ppm (Fe, C, 5 Zn treatments) yield decreased only by 30% and no signs of zinc toxicity appeared. These differences between observations could be explained by differences between concentrations of other metals in the soil and plants. Zinc toxicity must be connected more with the value of the Zn/Fe ratio in the plant than with Zn concentration alone. Results of the third experiment are shown in Figures 1 and 2. The initial absorption of phosphorus by ryegrass tops from sludge was very poor: after seven days of root soil contact the slope of the straight line representing P uptake from sludge (CO; S 1: S 3) was only about 15% of the monocalcium phosphate (CO; C 1; C 3)(Figure 1 ) . Afterwards, ratios between quantities of phosphorus absorbed by ryegrass from sludge or from monocalcium phosphate increased progressively (Figure 2 ) . After 2\ months phosphorus uptake by the tops of ryegrass from sludge was about 50% of that from monocalcium phosphate. These results can be compared with chemical extraction of phosphorus from the same sludge: 82% was extracted by citric acid, 47% by diluted sulphuric acid, but less than 1% by Ca Cl_.

143-

Monocalcium phosphate

Rate

Fig. 1.

P uptake by ryegrass tops after 7 days of root soil contact (confidence limits at 5%)

6th clipping

TIME

Fig. 2.

P uptake by ryegrass tops: C , C , C C = control treatments (Monocalcium phosphate) S , S , S q = sludge treatments = no phosphorus.

145-

4 . CONCLUSION The fraction of sludge phosphorus that is readily available for ryegrass is very low: about 15%. But there is a progressive release of phosphorus from sludge and absorption by plants: after 75 days, the studied sludge was about 50% as efficient as monocalcium phosphate for P uptake by ryegrass. Sludge was a source of available Fe and had an antichlorotic effect on maize, but it partially bound the soluble iron supplied. Insofar as sludge iron would be partly chelated by organic matter, it would be interesting to test the long term antichlorotic role of sludges applied on a chlorosis-generating soil. Sludge Zn is less plant available than Zn sulphate. Fe decreases Zn absorption by maize and the toxicity of absorbed Zn. Consequently, the Zn/Fe ratio in plants is a better toxicity indicator than Zn concentration alone. In practice, one might suggest using this antagonism to try to limit absorption and utilisation of heavy metals by plants.

REFERENCES

J u s t e , C. and Solda P., 1 9 7 7 .

Effets d'applications massives de boues de

stations d'epuration en monoculture de Mais: action sur le rendement et la composition des plantes e t sur quelques caracteristiques sol. S c i . S o l . , 147-155. Comparaison de 1'utilisation par le Mais du phosphore du

Pommel, B . , 1979.

des boues residuaires o u du phosphate monocalcique pour differents niveaux de zinc et de fer dans le substrat. Sommers, L.E., 1 9 7 7 . A n n . a g r o n . 30, 4 4 3 - 4 5 3 .

Chemical composition of sewage sludge and analysis of J. E n v i r o n . Q u a l . 6, 225-232. short-term

their potential use as fertilisers. Stanford, G. and Dement, J.D., 1 9 5 7 .

A method for measuring

nutrient absorption by plants: I, Phosphorus. 21, 6 1 2 - 6 1 7 . T a k k a r , P.N. and M a n n , M . S . , 1 9 7 8 . Maize and W h e a t ,

Soil S c i . Sty Proc.

Toxic levels of soil and plant zinc for

Plant Soil 4 9 , 667-669.

146-

DISCUSSION A. Cottenle (Belgium) I am very surprised when I look at Table 2 where iron has been applied and it is acting in an antagonistic way with zinc. We see a dramatic increase of zinc content in the plants, from 34 to more than 3 000 ppm. It is certainly a confirmation that zinc is very mobile and can be taken up in very different ways. However, the contents are extremely high here while the contents of iron being applied remain at the same level. Now, iron is always much less mobile in soils as well as in plants. It is also known that the iron content of plants may vary but within small limits. My question is, is it possible that in your experiments the available iron was very different to that without iron? The soil always contains a large amount of iron. If we add more iron to the soil or to the growth medium, it is very rapidly immobilised and rendered almost immobile. Have you any further explanation than this antagonism between iron and zinc? B. Pommel (France) The experiment was made with sand, not soil. A. Cottenie Yes, but even so, if you put iron sulphate in a solution at a pH of 6, 5 or 4, you can easily calculate from the solubility of iron hydroxides how much iron will be in that solution. You will not have even 1 mg of iron in a solution unless the pH is down to 3, 2 or 1. This is even more interesting if you work with pure sand. From the chemical point of view it is absolutely impossible that this iron should have been soluble. It is precipitated even at pH 4 or 5, unless there is a complexing agent that keeps it soluble. B. Pommel But you can see that there is a strong difference between the behaviour of maize in the first experiment without iron, and the second with iron.
- 147-

SEWAGE SLUDGE AS A PHOSPHATE FERTILISER S. de Haan Institute for Soil Fertility, Haren (Gr.), The Netherlands
ABSTRACT Plant availability = 100%. of phosphorus Phosphorus in normal sewage sludges with phosphorus sludges, chloride unavailable in chemical varied by of no obtained. phosphorus in

our experiments calciumphosphate treating ferric whereas negative effluent

from 20 - 100% in comparison or surface sulphate, water with ferric was practically agent

in mono-

obtained or a mixture to

and aluminium effect

plants,

lime as a dephosphatising on the availability literature than that point

seemed to have practically in the sludge of availability

of the phosphorus to a better experiments.

Data from recent in sewage sludges

found in our

149-

QUANTITIES OF PHOSPHORUS IN SEWAGE SLUDGE In the Netherlands the average production of sewage is 3 approximately 50 m /PE (population equivalent) per year, containing approximately 1 kg of phosphorus (P = 0.44 P^Oj.; P 2 5 = 2.3 P ) . After mechanical-biological treatment, 25% of the phosphorus is still present in the sewage sludge. Assuming a sludge production of 20 kg DM (dry matter) per PE per year, the P concentration in the dry matter would be approximately 1.25%. By additional chemical treatment, 90% or more of the phosphorus can be removed. In this case the P concentration in the sludge amounts to approximately 5% (of DM). In 570 sludge samples, analysed in the period 1972/76, the P concentration varied from 0.5 to 4.1%, with a mean value of 2.0%. Over 1967/70 the mean value was 1.6%. Apparently there is a tendency to increase in the course of time. A further increase in the future depends on the extent to which chemical treatment to remove additional P from sewage is introduced. On the other hand, legal measures are now in preparation in the Netherlands to phase out the use of detergents containing P, which may lead to a lower P concentration in the sludge. The amount of phosphorus in sludge currently amounts to about 0.4 kg/PE/year in the Netherlands. With 7 people per hectare of agricultural land this would mean an average supply of 2.8 kg P/ha, if all sewage was treated and all sludge was applied to agricultural land. However, only about 80% of the sewage is treated as yet, and only about 40% of the sludge is applied to agricultural land. Consequently, on average, only 1 kg P from sludge is available per ha of agricultural land per year. Corresponding values for P from fertilisers and animal waste are 20 and 30 kg, respectively. The contribution of sludge in the P-supply of agricultural land therefore currently amounts to less than 2%.

150-

DETERMINATION OF THE PLANT AVAILABILITY OF P IN SLUDGE IN COMPARISON WITH MONOCALCIUM PHOSPHATE OR SUPERPHOSPHATE Sludge, being an organic fertiliser, contains all other plant nutrients in varying amounts in addition to P. To determine the effect of P the effect of these accompanying nutrients has to be excluded or compensated. This is especially true for the N (nitrogen) effect, which is usually dominant. The effect of N on P uptake at the same supply of P is demonstrated in Figure 1. The data have been obtained from a pot experiment with a combination of five P application rates at five N application rates to ryegrass, of which five cuts were harvested and analysed for N and P. P was applied once at the beginning of the experiment. N-application was repeated for each cut. The effect of N on P-uptake was a combined effect of N on yield and P-concentration in the crop (De Haan, 19 80) . In contrast to the N effect on P uptake, there was hardly any effect of P on N-uptake. The effect of the other nutrients can be compensated by regarding sludge as a N+P+K+Mg+ minor-element fertiliser and comparing it with a fertiliser containing the same elements in mineral form. The elements should be present in the best possible proportions to meet the needs of the test crop; e.g. for grass the N:P:K:Mg ratio could be 1:0.5:1:0.3. Minor elements can be supplied, if necessary, in an amount sufficient to prevent deficiency. When the elements are not present in optimum proportions in sludge, they have to be supplemented with fertilisers in mineral form. For N in sludge only the mineral part is taken into account. In most cases the effect of the organic part is negligible. If there is an effect of the organic part, either negative or positive, the P effect has to be corrected for this effect. The practical execution of this concept will be demonstrated with an experiment in which the P effect of a sludge from a purification plant for calf slurry with lime as dephosphatising agent was studied.
151-

Pi

N-upt ake,mg N/pot 3600 3200

Pi

P2

2800
Pi

N3

2400 2000 P o 1600 1200 800 400 No 0 N1 N2 N3 Nt 1250 2500 3750 5000 mg N/pot

N2

Po 0

Pi 220

P2 440

P3 660

P* 880mgP/pot

Fig. 1.

Effect of a p p l i c a t i o n of nitrogen (as NHi,!*^) on phosphorus, and of a p p l i c a t i o n of phosphorus (as Ca (H2PO1,) 2) on n i t r o g e n , taken up i n f i v e c u t s of r y e g r a s s given the same a p p l i c a t i o n r a t e s of phosphorus and n i t r o g e n , r e s p e c t i v e l y .

PLANT AVAI LABI LI TY OF P I N SEWAGE SLUDGE FROM CALF SLURRY, TREATED WI TH LI ME FOR P-REMOVAL T h e e x p e r i m e n t was c a r r i e d o u t w i t h soil in Mitscherlich pots. (pH-KCl 4 . 3 4 ) harvested, r y e g r a s s on a sandy acid were Three c u t s

The s o i l w a s s l i g h t l y

and poor i n p l a n t a v a i l a b l e P .

w e i g h e d and a n a l y s e d f o r N and P . the sludge contained 7.35% P 1.75% mineral

On a d r y m a t t e r b a s i s (5.40% a s o r t h o - P , N, 1.76% K a n d 0.66% Mg.

the remainder as organic P ) ,

P i n t h e f o r m o f s l u d g e i n c o m p a r i s o n w i t h MCP (monocalcium phosphate) of t h e e x p e r i m e n t N ( a s NH NO,) was mixed t h r o u g h t h e s o i l i n a m o u n t s o f O, 220, 440, at the beginning 250, 6 6 0 a n d 880 m g / p o t .

a n d K ( a s K SO.) w e r e a d d e d i n a m o u n t s o f O,

152-

dry matter yield g/pot 70 r

P-uptake 400 monocalcium' phosphate sewage sludge

60

sewage sludge .monocalcium, ' ' phosphate

50

40 2 20 440 660 880 P-opplication rate, mg P/pot

30
_L

F i g . 3.

220

440 660 880 P-application rate, mgP/pot

Effect of phosphorus i n sewage sludge and as monocalcium phosphate on the amount of phosphorus taken up by English ryegrass.

Fig. 2.

Effect of a p p l i c a t i o n of phosphorus i n sewage sludge and as monocalcium phosphate on dry matter y i e l d of English r y e g r a s s .

500, 750 and 1 000 mg/pot, and Mg (as MgS0..7H 0) in amounts of 0, 75, 150, 225 and 300 mg/pot. Applications of N, K and Mg were repeated after the first and second cut. For the first cut the amounts of N, K and Mg applied with sewage sludge were deducted from those given in mineral form. The cumulative dry matter yield is presented in Figure 2. It is evident from this Figure that the yield was somewhat higher with sludge compared with MCP. Figure 3 shows that the contrary was true for P-uptake. Net uptake was about 25% for P from sludge and 30% for P from MCP. In Figure 4 the correction for the difference in dry matter yield has been carried out. P-uptake has been plotted against dry matter yield. With the same dry matter yield, the relationship between P-uptake from sludge and MCP is CD:BD, or about 90:100. At the end of the experiment, concentrations of watersoluble P in the soil were determined. Water-soluble P in mg/1 soil at a soil/water ratio of 1/60 is used in the Netherlands as a measure of plant-available P. The results are presented in Table 1. This table shows that the amount of water-soluble P in the soil with sludge was somewhat less than with MCP; this again points to a somewhat lower plant-availability of P from sewage sludge when compared with P from MCP.
TABLE 1 CONCENTRATIONS OF WATER-SOLUBLE P IN mg/1 SOIL AT THE END OF THE EXPERIMENT P application ra te. mg/got 0 Soil with sludge-P Soil with MCP-P 15.3 15.3 220 12.3 14.7 440 13.3 16.3 660 15.0 17.7 880 16.3 24.7

P-uptake,mg/pot 400 r B monocalcium phosphate 300 sewage sludge

200

100

30

40

50 60 70 dry matter yield, g/pot

Fig. 4.

R e l a t i o n s h i p between dry matter y i e l d and phosphorus in r y e g r a s s , s u p p l i e d with phosphorus as monocalcium phosphate and as sewage sludge.

PLANT AVAILABILITY OF P IN SEWAGE SLUDGE, OBTAINED BY CHEMICAL TREATMENT OF INDUSTRIAL WASTEWATER WITH FERRIC SULPHATE AS A COAGULANT The r e s u l t s of an e x p e r i m e n t w i t h t h i s that ferric sludge are as mentioned coaguThe

because they indicated effect factory styrene,

or aluminium s a l t s

l a n t s o r d e p h o s p h a t i s i n g a g e n t s h a v e a much m o r e on p l a n t a v a i l a b i l i t y s l u d g e came from t h e s e w a g e t r e a t m e n t p l a n t o f a (Hoechst Holland N.V., Breda) as very small p a r t i c l e s , acid. and a p a r t

negative polystyrene f r o m 60% p o l y it which nutrient

of P i n s l u d g e t h a n l i m e .

a n d 8% i r o n h y d r o x i d e , m o r e t h a n 90% o f

c o n t a i n e d 7.75% P i n t h e d r y m a t t e r , was s o l u b l e i n 2% c i t r i c in t h i s sludge.

P was t h e o n l y p l a n t

As P - f e r t i l i s e r in this

t h e s l u d g e was compared w i t h c r o p , which was

superphosphate harvested

e x p e r i m e n t on o a t s a s t e s t
- 155-

at ear emergence and analysed for P. P-uptake is presented in Figure 5. P-uptake from sludge amounted to only about 10% of that from superphosphate, due to a smaller effect on crop yield, but even more to a smaller effect on the P-concentration in the crop.
R. uptake, mg/pot 100r

90

'superphosphate

80

70

60

50

sewage sludge

40 110 220 330 U 0 ^application rate, mg/pot

F i g . 5.

Amount of phosphorus i n o a t s , supplied with phosphorus as superphosphate and as sewage s l u d g e .

EXPERIMENT WITH 15 DIFFERENT SLUDGES

This experiment was c a r r i e d out in 1975. The sludges a r e , in the a l p h a b e t i c a l order of the names of t h e i r places of o r i g i n , l i s t e d in Table 2, together with the r e s u l t s of the experiment. Sludges 1, 3, 4, 5, 9, 10 and 12 came from normal mechanical-biological treatment p l a n t s for domestic and mixed wastewater. Sludge 3 took a somewhat d i f f e r e n t p o s i t i o n in t h i s

156-

TABLE 2 MEAN RELATIVE VALUES (MCP = lOO) FOR 15 SEWAGE SLUDGES FOR DRY MATTER YIELD, P-UPTAKE WITHOUT AND WITH CORRECTION FOR DIFFERENCES IN DRY MATTER YIELD, AND CONCENTRATIONS OF WATER-SOLUBLE P AT THE END OF THE EXPERIMENT, AFTER SUBTRACTION OF THE VALUES FOR CONTROL (= WITHOUT P) . ABSOLUTE VALUES FOR MCP IN PARENTHESES (DM : g/pot; P UPTAKE : % OF P SUPPLY; WATER-SOLUBLE P IN SOIL : mg/1).

Dry matter yield

P--uptake

Water-soluble P i n s o i l

with without c o r r e c t i o n for d i f f e r e n c e i n dry matter y i e l d 100 (19.0)

36 54 38 46 24 40 41 32 65 90 17 51 4

Monocalcium phosphate 1 . Assen 2. Asten 3. Deidesheim (FRG) 4 . Delden 5. Eindhoven 6 . Elburg 7. Gieten 8 . Harderwijk 9 . Leiden 10. Oosterwolde 1 1 . Rijsenhout 1 2 . Tilburg-Oost 1 3 . Harderwijk 14. Svedala (Sweden) 15 . Schuilenburg

lOO (7.66)
105 185 72 144 169 34 104 144 183 134 185 90 44 10 103

lOO (19. 0)
34 29 52 32 14 118 40 22 36 68 9 57 8

lOO (11)
14 0 0 0 14 14 0 0 28 28 0 7

- 7 - 21 - 21

- 13
0

- 1
O

series, because after mechanical dewatering and mixing with sawdust (1:1) it passed a composting process in a so-called bioreactor. Sludges 2, 6, 7, 8 and 11 came from treatment plants with additional chemical treatment to remove P by means of ferric chloride or a mixture of ferric and aluminium sulphate (sludge 2). The only sludge which with certainty has been affected by the dephosphatising process is sludge 11, with an iron content of 15%. Sludges 13 and 14 were pure chemical sludges, obtained by treating the effluent after mechanical-biological purification with ferric chloride (13) or a mixture of ferric and aluminium sulphate (14). Sludge 15 came from a pilot plant to purify surface water for drinking water purposes, using ferric chloride as a flocculating agent. The sludges were air-dried and mixed with a sandy soil in amounts corresponding with 0, 220, 440, 660 and 880 mg P per Mitscherlich pot and with the same amounts of P as MCP. N, K, Mg and minor elements were applied in the same optimum amounts at all P application rates. N in sludges was compensated for by assuming an efficiency index of 30% for total N in the sludge. When N-supply from sludges appeared to be higher or lower than the assumed amount, a correction could be made for yield and P-uptake, because each MCP rate was applied at five mineral-N rates, ranging from 0 to 1 000 mg N/pot. The test crop was English ryegrass, of which five cuts were harvested and analysed for N and P. Fertilisation with mineral N was repeated for each cut, K and Mg fertilisation from the third cut. At the end of the experiment concentrations of water-soluble P in the soil were determined. Table 2 shows dry matter yields obtained with MCP and the different sludges, as well as P-uptake, without and with correction for yield differences, and concentrations of watersoluble P in the soil at the end of the experiment.
- 158-

Table 2 shows that DM yield for most (10 out of 15) sludges was higher for sludge than for MCP. For P-uptake however, all values were lower for sludge than for MCP, except for one sludge after correction for difference in yield. Concentrations of water-soluble P in the soil at the end of the experiment were also lower for sludges in comparison with MCP. There were large differences among sludges. In comparison with MCP-P = 100%, P-uptake for normal sludges (1 - 12) ranged from 36 - 90% for sludges without and from 17 - 54% for sludges with additional P-removal from the sewage by means of Fe- and Al-salts. After correction for yield differences the mean values of P-uptake without and with additional P-removal from the sewage were not significantly different. Uptake of phosphorus from the pure chemical sludges (13 - 15), however, was practically nil, indicating that additional P, obtained by treating sewage of effluents with ferric and aluminium salts, may not be available to plants. For the normal sludges, the mean value for P-uptake, measured in five cuts of English ryegrass, was 40 - 50% of MCP-P. The absolute value for MCP-P was about 20%. From the concentration of water-soluble P in the soil at the end of the experiment it can be concluded that there may be a residual effect for MCP-P, but not for P in sludges. DISCUSSION In our experiments plant availability of phosphorus in normal sewage sludges varied from 20 - 100% in comparison with phosphorus in monocalciumphosphate = 100%. Phosphorus in chemical sludges, obtained by treating effluent or surface water with ferric chloride or a mixture of ferric and aluminium sulphate was not available to plants. The effect of lime as a dephosphatising agent on the availability of phosphorus in the sludge obtained was very small.

159-

Our conclusion that availability of phosphorus in sewage sludges is rather low and variable, is in agreement with that of Platzen (1974) on the basis of a review of results then available. In general a better availability of phosphorus in sewage sludges, even in those obtained by treating sewage or effluent with aluminium and/or ferric salts, has been reported by Cervenka and Timmermann (1976), Werner (1976), Gleisberg and Taubel (1978) and Gupta and Hani (1979). Variation among the results of different authors may be due to variation in the dry matter content (drying has a negative effect on availability of P in sludges; cf. Furrer, 1977) the heavy metal (especially iron) content, characteristics of the soil to which the sludge is applied, the test crop, the duration of the experiment and last, but not least, an inadequate compensation of the nitrogen effect of the sludges. No doubt, if sewage sludge is to be used as a phosphate fertiliser, more research about the availability of its phosphorus will be necessary.

-160-

REFERENCES Cervenka, L. and Timmermann, F., 1976. Landwirtschaft. Furrer, J., 1977. Phosphatfallungsprodukte aus

biologisch geklarten Abwassern und ihre Verwendungsmttglichkeit in der Landwirtsch. Forsch. Band 29: 299-308. Dokumentation InformSchweiz. Der Dtlngewert des Klarschlamms.

ationstagung "Klarschlammverwertung in der Landwirtschaft". Landw. Technikum Zollikofen: 13-26. Gleisberg, D. and Taubel, N., 1978. Boden 1, 5-8. Gupta, S.K. and Hani, H., 1979. of sewage sludges. Haan, S. de, 1980. Platzen, H., 1974.

Zur Phosphatwirkung von Schlammen avis Wasser und

der kommunalen Abwasserreinigung mit Phosphatfallung.

Estimation of available phosphate content

Proc. European Symposium on Characterisation and

Use of Sewage Sludge, Cadarache, France. De fosfaatwerking van zuiveringsslib en stadsvuilcompost. Phosphatzufuhr und Ausnutzungsraten von aufbereiteten Die Bedrijfsontwikkeling 11, 2: 195-202. Siedlungsabfalien am Beispiel von Vegetationsversuchen. Phosphorsaure 30 (2): 219-246. Werner, W., 1976. Untersuchungen zur Phosphatwirkung von Klarschlammen Landwirtsch. Forsch. Sonderh. aus der chemischen Abwasserreinigung. 32/1: 177-185.

1 6 1

DISCUSSION
M. Webber (Canada)

If I recall correctly, your sludge treatment yields were almost always higher than the monocalcium phosphate treatment yields, and yet the P uptake for monocalcium uptake was higher. Does that mean that there was more phosphate taken up from the monocalcium phosphate treatment than was needed by the plants?
S. de Haan (Netherlands)

If the plants are supplied with more phosphate than they actually require then they will take it up, within limits, of course. M. Webber But if you have, in fact, luxury consumption of phosphorus from the commercial fertiliser treatment, is this necessarily a good comparison? S. de Haan The farmer wants to know how far to reduce fertilisation with superphosphate or basic slag if he is using sludge so we have to answer this question.

162-

EFFECTS OF SLUDGE PROCESSING ON SOIL PHOSPHORUS MOBILITY MEASURED WITH THE ISOTOPIC DILUTION KINETICS METHOD J.L. Morel Service Science du Sol, Ecole Nationale Superieure, d'Agronomie et des Industries Alimentaires, 38, rue Sainte Catherine, 5 4000 Nancy, France. ABSTRACT The isotopic on soil soil samples dilution-kinetics issued from: with (fj/R, except method described phosphorus experiments by Fardeau et al ., value. sludges; sludge interest: 2) the It was 2) long of the applied acidic in which an

1978j was used for the study was incubated

of the sludge 1) laboratory

for two months with

six different that special

term field the kinetic soil related spreading of soil process excess

experiments parameters mobility

an urban limed sludge. n, p) indicated with

The determination increased 1) the with

phosphorus

when it was lime treated.

The problems the

to limed sludges of their rates and these of calcium of sludges

were studied effects and with effects

importance

negative mobility

was shown to be connected the loading diminished deficient rates;

reduction as the of

phosphate-ion

did not appear to be an It is suggested on soils that in

irreversible

detrimental disappeared. be avoided

over the years landspreading

limed sludges

should

phosphorus.

163-

INTRODUCTION Although the high phosphorus content of sewage sludge is now established (Anderson, 1959; Morel, 1978; Sommers et al. , 1976) , its availability to plants has not yet been well determined. This partly depends on the various compounds in which phosphorus is included and on its different solubilities. (Sommers et al., 1976; Dean, 1973). However, for agricultural use of sludge it is as necessary to know the fertilising phosphorus value as the nitrogen value. This value can be found in several ways such as the determination of: - Sludge phosphorus availability index by using chemical extractors on soil : sludge mixtures or directly on sludge. - The effect of spreading sludge on soil phosphorus mobility, with this method, instead of testing a quantity of phosphorus, the possible modifications of phosphorus specific parameters of soil due to the addition of sludge, such as the fixation capacity for phosphate-ions, are considered. We have chosen the second approach to this problem. For this purpose we used the isotopic dilution-kinetics method devised by Fardeau and Jappe, 1978; Fardeau, 1979, on soil samples taken from laboratory and field experiments set up to study the agronomic qualities of different sludges, especially limed sludges. METHODS Isotopic dilution kinetics method With the isotopic dilution kinetics method (Fardeau et al., 1978; Fardeau and Jappe, 1978; Fardeau, 1979) a measurement of kinetic parameters of phosphate-ion mobility in soil
164-

is given, and the consequences of soil agronomic treatments, such as sludge spreading, are indicated. 32 An amount (R) of radio-activity is injected as PO. carrier free in a soil solution system (1 : 10) after 17 hours of agitation and the evolution of the solution ratio activity (r) is measured as function of time. The evolution of the phosphate ions specific radioactivity in the solution decreases with time and can be described by the following general empirical equation:

R =

Hi
R

. t~n

r l where -g- ratio of the solution radioactivity after 1 mn of isotopic exchange represents the soil fixation capacity for phosphate-ions.

t = time n = a soil specific characteristic p = the phosphate-ion concentration in the solution because of agronomic treatments these kinetic characteristics show variations due to agronomic treatments, as indicated in Table 1. TABLE 1 EVOLUTION OF KINETIC PARAMETERS DURING THE MODIFICATION OF SOIL Soils in a period of Phosphorus enrichment Phosphorus impoverishment 1/R

' >

\ /

/ \

165-

Other soil chemical analyses pH: measured in a 1 : 2.5 soil solution mixture by the electro-metric method. Organic carbon: 12 apparatus. determination with the carmhograph

Available phosphorus: in acidic soils use of the DYER method (2% citric acid). Calcium concentration in soil solution: determination by using an atomic absorption spectrophotometer. MATERIALS Soil samples were taken from the following two experiments; In the first, an acidic silty soil was mixed with six different sludges at agricultural rates then it was incubated at 28 C for two months. These sludges were prepared as shown in Figure 1 (Colin, 1979). aerobic , , ^r / raw-sludge ^anaerobic ^ digestion ^ ^^ ^*w t

flocculation by liming 3 flocculation by liming " j " , FeC1 3

thermic treatment (180C)

^""^

Fig. 1. Preparation of the sludges for the incubation experiment. The second was a field experiment located in La Bouzule (Meurthe et Moselle, France), where we have been studying the agronomic properties of an urban limed sludge since 1974. The soil samples analysed for their phosphorus mobility have been collected annually from four plots. The chosen plots were treated as indicated in Table 2.

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TABLE 2 PLOT TREATMENTS Limed sludge Control treatment Total sludge applied between 1974 and 1980 (t/ha DM) Number of applications 1 (LSI) Limed sludge 2 (LS2)

100

200 4

Dates of sludge applications

1974

1975

1976

1977

1978

1979

1980

RESULTS AND DISCUSSION 1. Consequences of sludge processing on the phosphorus mobility of an acidic soil

The results obtained from the analyses of the incubated soils are shown in Table 3. In this experiment, the sludges added from 190 to 280 ppm of total phosphorus to the soil. This greatly influenced the level of the citric acid extractable soil phosphorus which was approximately 10 times that of the control soil. Taking into account the sludge phosphate value due to the increase of DYER phosphorus, 35% to 60% of total sludge phosphorus was then available. Furthermore, it should be noted that the lowest efficiency was with limed sludges. However, looked at with the isotopic dilution kinetics method, the consequences of sludge spreading on soil phosphorus r appeared slightly different. The increase of the 1/R value for four sludges indicated that the fixation capacity for phosphate-ions was reduced by sludge application (control soil: r l/R = 0.32; soil + sludge: rl/R = 0.37 to 0.40). This confirms
167-

that sludge is a material which is able to improve soil phosphorus fertility, particularly by its supply of organic matter. However, we observed, as did Fardeau et al. (1978), that limed sludges greatly reduced the mobility of soil phosphate-ions; here 1/R showed an important decrease with the limed + FeCl3 sludge (pH 11.2). The problems concerning limed sludge are discussed in the second part of this paper.
TABLE 3 SOIL PHOSPHORUS MOBILITY AFTER INCUBATION WITH SIX TYPES OF SLUDGES Control soil Raw sludge Thermic sludge Aerobic sludge Anaerobic sludge Anaerobic Anaerobic limed + sludge FeCl 3 sludge 6.6 0.292 0.313 0.352 6.9 0.209 0.245 0.360

pH

5.2

5.9 0.315 0.404 0.360

5.7 0.294 0.369 0.362

5.9 0.320 0.367 0.359

5.8 0.309 0.390 0.333

Available 0.036 P20 (DYER) (/ ) oo

r

l/R n

0.318 0.463

Furthermore, when the sludge was processed by digestion or autoclavage its influence on soil phosphorus mobility was modified and rather less effective than raw sludge. This was probably due to the transformation of the organic material during processing and suggested that the form of organic matter added to the soil plays an important role on its phosphorus fertility. 2. Problems related to limed sludges

The application of limed sludge to the soil, even to an acidic soil, reduces phosphate-ion mobility. In the following we will examine two aspects of that problem: I. Influence of the loading rates. II. Duration of the effects. For this purpose, as described in 'Materials' we chose to analyse soils taken from a long term field experiment.

168 -

a) Loading rates The effects of the two limed sludges, on the soil kinetic parameters (Table 4) are quite different. Possibly this is due to the liming rates, as shown by the different pH of the sludges and also to the addition of iron chloride.
TABLE 4 EFFECT OF THE LIMING RATE ON SOIL KINETIC PARAMETERS
I

Soil treatments

Sludge pH

Sludge Fe ppm

l/R

Ugp/g

Control Anaerobic digested sludge + lime Anaerobic digested sludge + lime + Feci,

9.90 11.2

19 740 43 400

0.318 0.313 0.245

8.1 3.0 1.7

The results of the kinetic analyses of soils from the field experiment plots indicated that the decrease of soil phosphate-ion mobility was related to the sludge loading rates (Table 5 ) .
TABLE 5 KINETIC PARAMETERS OF A SOIL ENRICHED WITH TWO RATES OF LIMED SLUDGE Plots Loading rate t/ha DM Control Limed sludge 1 Limed sludge 2
r

l/R

P pgP/g

pH

70 ( * ) V ; 140 l '

0.234 0.163 0.087

0.334 0.300 0.384

10.0 8.8 3.8

6.92 7.80 7.81

( * )

Three applications.

-169-

b) Duration of effects Results related to the soil kinetic parameters of the three plots at different periods are shown in Figure 2 and Table 6. These values varied slightly for the control soil due, it is thought, to the heterogeneity of the plot. However, for the LS2 treated plot the 1/R ratio showed an increase during the period without any application of sludge. Simultaneously the n and p characteristics decreased and increased respectively. This suggests that the reduction of soil phosphate-ion mobility by limed sludge applications is not an irreversible process. The variations of the parameters ( l/R, n) seemed to converge to a limit value which is probably the initial soil value. But for 1/R the time required to reach this value will certainly be long. This is supported by the fact for the LSI treated plot the evolution of the characteristics was very slow.

TABLE 6 EVOLUTION OF THE SOIL KINETIC PARAMETERS Date of soil sample

r

l/r LS2 C

n LSI LS2 C

P LSI ygP/g LS2

LSI

1975 1976 1977 1978 03/1979 10/1979 1980

0.248 0.234 0.246 0.236 0.234 0.163 0.180 0.184 0.181 0.184

0.062 0.087 0.136 0.155 0.169 0.149 0.154

0.294 0.334 0.294 0.319 0.306 0.300 0.301 0.292 0.280 0.308

0.384 0.384 0.367 0.341 0.313 0.332 0.299

12.8 10.0 15.4 10.2 12.6 9.1 12.2 10.2 13.0 11.9

5.6 3.8

7.8 12.2

11.7

C = control plot; treated plot.

LSI = limed sludge 1 treated plot;

LS2 = limed sludge 2

170-

1/R
i

Control

* *

* *

V
*
+ 60 t/ha (LS2)

0.20 "

LSI

y-

0.15 _ + 140 t/ha (LS2)

V
LS2

0.10 1 1

f*

A
1

0.05 -

1 1975

1976

1977

1978

1 1979

1 1980

Fig. 2. Evolution with time of the 1/R ratio. Furthermore, when the soil received a new rate of sludge (in March 1979) we observed a break in the evolution ( 1/R decreased, n increased) and then a start for a new one towards the limit value. In order to understand the modifications of phosphorus mobility in limed sludge-treated plots the soils were analysed for pH, organic carbon content and soluble calcium. The results (Table 7) indicate a constant pH during the six years
171 -

while the organic carbon content and the calcium concentration of the soil solution were decreasing with time. Calcium showed r 2 a high correlation with the 1/R characteristic (r = 0.95).
TABLE 7 EVOLUTION OF SOIL pH, ORGANIC MATTER CONTENT AND SOLUBLE CALCIUM IN LS TREATED PLOTS 1975 LSI pH LS2 7.84 7.80 1976 7.80 7.81 1977 7.87 8.00 1978 7.85 7.95 03/1979 7.93 7.97 10/1979 7.90 7.90

%
TOC LSI LS2

. -

2.25 3.50

1.92

2.08 2.57

2.08 2.30

ppm -

2.52

Ca

LSI LS2

47.14 240.07

52.06 213.05

42.25 47.35

36.98 42.70 30.90

33.26 37.15

LSI = limed sludge 1-treated plot;

LS2 = limed sludge 2-treated plot.

The data indicated that in the fresh limed sludge phosphorus is present in non-soluble form linked with calcium. Moreover when applied to the soil the excess of calcium in the sludge led to an increase of the soil fixation capacity for phosphate-ions. However, during cropping without any sludge application (from 1975 to March 1979) the calcium content decreased by leaching through the soil and through uptake by plants. This, combined with the mineralisation of organic matter which was previously protected by calcium (Morel et al., 1977), led to a reduction of the fixation capacity and simultaneously to a release of phosphorus in the soil solution. From an agronomic point of view, limed sludges could be used as soil organic fertilisers, if they are not spread at high rates, especially on soils poor in phosphorus where depressive effects on crops would probably be observed. One
- 172-

might suggest reducing the liming rate for the sludges intended for agricultural land. This would not affect sludge drying properties (Colin, 1979). In addition to this we should pay attention to the problem related to heavy metals which could use the same route as phosphate-ions and become more available to plants especially when they were accumulated in the soil surface by high loading rates of an urban limed sludge (Legendre, 1978). CONCLUSIONS The isotopic dilution-kinetics method described by Fardeau et al. (1978) was applied to the study of the sludge phosphorus value. Except when it is lime-treated, sludge increased soil phosphorus mobility. However, processing such as digestion and autoclavage tends to reduce the phosphorus value. However we were not able to determine precisely whether the differences between processed sludges were significant. Nevertheless we will try to apply this general method in order to classify sludges in relation to their own kinetic parameters. The information gained by a long term field experiment showed that the initial negative effects of limed sludge on phosphateions mobility were progressively reduced through the years. The decrease of the soil calcium content was in this case thought to be the most important factor of the phosphorus fertility increase. This means that limed sludge should not be spread at high rates on soils poor in phosphorus. However, more data are still needed on the influence of sludge processing methods such as flocculation (lime, FeCl,, A1 2 S0 4 , polyelectrolytes) and more generally on the influence of the type of organic matter on the mobility of phosphate and heavy metals in the soil.

173-

REFERENCES

Anderson, M.S., 1959. Colin, F., 1979.

Fertilising characteristics of sewage sludge.

Sewage

and Industrial Wastes, 31, 678. Co-ordination des travaux de recherche proposes par le C.R. fin de contrat - Ministere Groupe de travail Boues residuaires. Dean, R.B., 1973. options?

de 1'Environnement et du Cadre de Vie. Disposal and Re-use of sludge and sewage: What are the Proc. Conf. on Land disposal of Municipal Effluents and Cinetique de Dilution istopique et phosphore Projet de memoire de these d'Etat. Analyse par dilution istopique de la

Sludges E.P.A., 902/9, 73-001. Fardeau, J.C., 1979. assimilable du sol.

Fardeau, J.C. and Jappe, J., 1978. du Quebec.

fertilite et de la fertilisation phosphoriques de quelques sols Canadian J. of Soil Science, 58, 251-258. Repercussions de residuaires sur la mobilitie de Cd, Cr, Hg, Ier Symposium Sol et Dechets Solides Fardeau, J . C , Guiraud, G. and Hetier, J.M., 1978. l'epandage de boues

Zn et P dans les sols. Orleans. Legendre, A., 1978.

Consequences de l'epandage de boues residuaires

urbaines sur le profil du sol apres quatre annees d'experimentation D.E.A. Univ. Nancy. Morel, J.L., 1978. Boues residuaires et fertilisation phosphatee. Biodegradation et Humification. Sc. du Sol, Bull. Phosphore et Agriculture, 32_, 73, 15-22. Morel, J.L., Sedogo, M. and Jacquin, F., 1977. IV. Influence de la technologie d'epuration sur l'evolution d'une boue residuaire urbaine incorporee a un sol neutre. AFES, 3_, 157-166. Sommers, L.E., Nelson, D.W. and Yost, K.J., 1976. chemical composition of sewage sludges. 5,3, 303-306. Variable nature of J. Environ. Quality,

174-

DISCUSSION A Cottenie (Belgium) In your paper you indicate that p = the phosphate ions concentration in the solution. Is that in the soil solution or in your extract of 2% citric acid? J.L. Morel (France) It is in the soil solution - the water extract. A. Cottenie Was there a special reason for you to take the citric acid method for the estimation of status of phosphorus in soils? J.L. Morel In France we have two methods for the determination of soil phosphorus availability, one for acidic soils and one for neutral and alkaline soils. This was an acidic soil so I used that method.

175-

AVAILABILITY OF PHOSPHORUS FRACTIONS IN SEWAGE SLUDGE H. Hani, S.K. Gupta and O.J. Furrer Swiss Federal Research Station for Agriculture Chemistry and Hygiene of Environment, 3097 Liebefeld-Berne, Switzerland. ABSTRACT Using the Chang and Jackson phosphate Citric sludge similar it could be shown that two extractants phosphate. way to basic procedure in fractionating with the P uptake of plant sludge dissolved of by the plants. phosphate in a

the sum of the phosphate for the estimation that

NH.Cl + NH.F is correlated Since, solvent slag. in general,

acid is also appropriate

available

more than 70% of the total sludges may be judged

is found in this

it is concluded

177-

1. INTRODUCTION As far as can be ascertained, there has not yet been a detailed characterisation of sludge phosphate. Such information would be quite useful, because the availability of sludge phosphate reflects its nature and its form in sludge. However, this material is a diverse mixture of inorganic and organic compounds and thus poses several problems as to the exact delineation of various possible forms of sludge phosphate. The direct identification of sewage phosphate either by infra-red or X-ray analysis is complicated due to the presence of a large excess of organic and inorganic compounds. Furthermore, the use of powder X-ray diffraction techniques is limited to cases where the relevant compounds amount to at least 5%. The difficulties cited above (many more of which can be expected if direct evaluation procedures are to be employed) suggest a need to look for some indirect techniques for the characterisation of sewage phosphate. Considering the fact that the inorganic compounds of sewage sludge which contain principally the elements Al, Si, Fe and Ca, are similar to those found in the soil, we decided to use a successive extraction technique proposed by Chang and Jackson (1957) for the characterisation of soil inorganic phosphorus. Since then this technique has gained a considerable but by no means universal acceptance. Thus, a discussion concerning the successive extraction procedure (as proposed by Chang and Jackson, 1957) is presented in the following paragraphs. The authors suggested five extractants: 1. 2. 3. 4. 5. I N NH.C1 (water soluble and easily exchangeable) 0.5 N NH4F (Al-bound) 0.1 N NaOH (Fe-bound) 0.5 N H 2 S0. (Ca-bound) Sodium dithionite (reductant soluble iron-bound).
178-

In order to select the sequence of the extractant the authors used the minerals Strengite, Variscite and Apatite as reference sources. The authors observed that: 1. Ammonium fluoride dissolves aluminium phosphate completely, whereas iron phosphate is slightly dissolved. Calcium phosphate shows no reaction with NH 4 F. Sodium hydroxide dissolved completely both aluminium phosphate and iron phosphate. Again calcium phosphate did not react. Sulphuric acid dissolves calcium phosphate completely with simultaneous dissolution of aluminium and iron phosphate.

2.

3.

The authors thus decided that the fluoride and NaOH must precede the H-SO. extraction in order to obtain complete separation of these three chemical forms of phosphate. Several papers on the subject of the Chang and Jackson procedure have so far been published and most of them question the exactness of delineation of iron and aluminium bound phosphate. Several modifications on the procedure have therefore been proposed. Fife (1959a; b) suggested the use of a fluoride solution sufficiently alkaline (about pH 8.5) to inhibit resorption of phosphate by free iron oxides. Another basic weakness of the Chang and Jackson approach arises from a possible adsorption of phosphate on oxide surfaces (or from its accumulation on the surface of solid mixed phosphates such as Fe(OH) (P0 4 ) 3 _ x y 3 ) which could participate in surface reactions by ligand exchange (Gupta, 1976). Bromfield's studies (1967a; b) with fully phosphated iron oxides, especially haematite, showed that a large fraction of iron oxide-bound phosphorus was released in the ammonium fluoride solution. It is reasonable to conclude from this that fluoride reagent not only releases phosphate by forming complexes with
179-

aluminium compounds but also by exchange with the phosphate bound on the surface of compounds rich in iron and aluminium. The release of more strongly bound phosphate either adsorbed on iron oxhydroxide or in the bulk of crystal-line iron phosphates is affected by the presence of NaOH (Gupta, 1976). The phosphate which is not extracted by NH.F, NaOH and H2SO. is designated as 'reductant soluble phosphate'. This fraction originates from the phosphate occluded within the matrices and in the pores of hydrated iron oxyhydroxide compounds such as Goethite (a-FeOOH) and lepidocrocite (y-FeOOH) etc. Even if these fractions found in the different extractants do not represent chemically well defined phosphate forms, the release of phosphate by the anions CI , F and OH seems to be a useful attempt to identify phosphates of increasing bonding strength in the sludge. It should therefore be possible to find a suitable extractant from amongst NH.C1, NH.F and NaOH (H-SO. is omitted because phosphate removed by this solvent is not likely to become plant available within a short time) in order to determine the plant available phosphate content of a sludge. However, the described fractionation scheme may be too laborious for routine work. This is .why the citric acid method, well known in the analysis of fertilisers, has also been tested. 2. MATERIALS AND METHODS The exact method of fractionation of P and its determinatio were described elsewhere (Gupta, 1976; Gupta and Hani, 1979; Hani and Gupta, 1978). For the growth experiment an acid sandy loam (Liebefeld soil of pH 5.3) and a limed Liebefeld soil of pH 7.3 were used. Italian ryegrass was taken as the test plant. The characteristics of the sewage sludges used in the pot experiment are given in Table 1.

- 180-

TABLE 1 CHARACTERISTICS OF SEWAGE SLUDGES USED Total P mg/g* % of the Total P content 2% citric acid 90.8 Cl+F C1+F+0H Total Fe mg/g* Total Al mg/g* Total Ca mg/g*

Sludge

Remarks

Z o B'df

14.2

69.6

,3.5

7.75

17.8

193

Undigested; no chem. treatment Digested; no chem. treatment Digested; no chem. treatment Digested; no chem. treatment Digested; no chem. treatment Undigested;Eeprecipitation Digested; Feprecipitation Digested; Feprecipitation

17.1

69.5

60.5

65.6

12.1

40.0

76.6

Aa

26.2

81.8

67.4

69.9

15.0

88.0

Bl

27.3

40.2

32.8

85.8

54.0

31.0

89.4

L'th

14.7

79.1

73.8

77.7

7.65

62.0

87.2

33.0 22.9 18.4 49.1

99.5 26.2 ICO 85.2

33.1 18.2 67.4 45.1

69.7 61.3 70.5 53

33.1 62.0 23.8

11.5

147 55.1

Bae Wl Pf

69.8

Digested; Alprecipitation

Expressed as mg of P, Fe, Al and Ca per g of sludge dried at 105C (dry matter). With the exception of sludge W l , which is used as wet sludge, all other sludges have been dried at 105C before being added to the soil.

1 8 1

3. RESULTS AND DISCUSSION 3.1. Successive extraction of some well defined non-aged iron precipitates One attempt to characterise sludge phosphate is made by its comparison with well defined phosphate compounds. As Fe(III) salts received the widest use in the elimination of phosphate, iron phosphates were chosen for this purpose.
TABLE 2 PERCENT DISTRIBUTION OF TOTAL EXTRACTABLE PHOSPHATE, IRON AND CALCIUM IN SUCCESSIVE EXTRACTION OF PHOSPHORUS COMPOUNDS (Gupta, 1976) Phosphorus compounds ( % of the total extractable element) Sludge (Wl) NH 4 C1 P Fe Ca NH 4 F P Fe Ca NaOH P Fe Ca P Fe Ca Na2S204 (reductant soluble, iron bound) P Fe Ca 34.6 2.4 53.6 42.8 39.3 3.6 2.4 2.8 18.6 45.8 43.6 0.5 10.1 Al (amorphous) 1.1 0.02 17.2 3.2 79.2 0.02 2.3 96.6 1.33 0.13 CIP (cystalline) 0.1 0.02 l.Ol 4.4 95.8 0.017 2.8 95.4 0.11 0.16 -

Extractant

Element

2 S 4

182-

The results shown in Table 2 indicate that 35% of the total extractable phosphate of sludge Wl is present in NH.C1. At the same time 53.6% of the total extractable calcium is dissolved in this solvent, suggesting that a considerable amount of phosphate is bound to calcium. Although sludge Wl originates from a waste water plant with iron precipitation only a small amount of phosphate may be bound to iron because not more than 3.6% of P is present in the NaOH solution. However, this figure corresponds with the comparatively low Fe content (Table 1) which could mean that iron precipitation was not complete in this plant. In contrast, AIP and CIP have 79 and 95.8% of the total extractable phosphorus in the NaOH extract. Differentiation between AIP and CIP is possible due to the different amount extracted by NH 4 F. The AIP has about 17.2% of the total extractable phosphate in this extract whereas CIP has only 1%. 3.2. Successive extraction of different sludges The results shown in Table 2 may indicate something of importance when looking for plant available phosphorus fractions in sewage sludge. According to this Table, crystalline iron phosphate releases its large fraction of phosphate in the NaOH solution. As the P utilisation of this source is very low (Gupta, 1976) it is likely that the efficiency of sewage sludge phosphate is over-estimated by the inclusion of this solvent. Figure 1 shows that there is only a small variation in the sum of the CI , F and OH -soluble phosphate of the nine sludges used in the pot trial, whereas the phosphate dissolved by citric acid ranges from 20 to 100%. From Table 1 which gives the exact values of Figure 1 it is further evident that the highest portion of OH soluble phosphate is found in sludges with the highest amount of iron. If the NaOH soluble fraction is omitted an acceptable correlation (r = 0.628) is obtained between the two remaining fractions and the citric acid soluble phosphate (see Figure 1). However, one sludge (L ) lies far below the regression line, suggesting that citric acid may also
183-

10 Fig. 1.

20

30

40

50

~?0~

7 ' 0

80

90

100

K> P c i t r i c

acid

Relationship between citric acid and Cl

+ F -soluble phosphate (r = 0.628),

dissolve strongly bound sludge phosphate. This assumption is strengthened by the fact that burned sludges (at 800C) often show a solubility between 30 and 60% in citric acid whilst less than 10% are dissolved in the three extractants NH.C1, NH.F and 4 ' 4 NaOH. One cannot therefore rule out the possibility that citric acid, due to its complexing ability, attacks a certain amount of phosphate which is assumed to be soluble only in aggressive solvents such as sulphuric acid. In order to substantiate the relationship found to exist between citric acid, and CI +F -soluble phosphate a statistical interpretation was carried out on the necessary analytical data from 28 sludges (including burned sludges). With a correlation of r = 0.694 the expected trend was confirmed, demonstrating that most of the points under the regression line (deviation due to a comparatively large amount of phosphate dissolved in citric acid) belong to iron rich sludges together with their ashes. 3.3. Relationship between relative % phosphate utilisation of different sludges and soluble sludge phosphate According to the results of the preceding paragraph two solvents, namely citric acid and the combination of NH.C1 and NH.F, may be suitable for finding a relationship between soluble sludge phosphate and plant uptake. As can be seen from Figures 2 and 3 there is a correlation of r = 0.9 4 for citric acid and of 0.866 for Cl~ + F between extracted P and relative % P utilisation in the acid soil (pH 5.3). However, this correlation is much lower in the limed soil (pH 7.3). At the same time the relative % P utilisation decreases by 10 to 30% compared to the values in the soil (Table 3 ) . The deviation of the sludge L from the regression line shown in the diagram with citric acid (Figure 2) may be due to the fact, already mentioned, that in some sludges this solvent also tends to dissolve strongly bound phosphate which is not thought to become plant available with a short time.
185-

Relative V

utilization

Fig. 2.

Relationship between citric acid soluble P ( % of total P) and relative % P utilisation of different sewage sludges (r = 0.94) .

_ X ( c i t r i c acid soluble P)

10

100

y Relative'/iP

utilization

100

50

Fig. 3.

Relationship between Cl~ + F~ soluble P ( % of total P) and relative % p utilisation of different sewage sluges (r = 0.87).

1 0
I l _
1

'

10

50
186

1 0 0

Xf cl + F soluble P)

TABLE 3 RELATIVE % P UTILISATION, 2% CITRIC ACID, AND Cl~ + F~-SOLUBLE P (AS % OF THE TOTAL) PLANT: ITALIAN RYEGRASS Relative % P utilisation Sludge 2% citric acid soluble 90.8 69.5 81.8 40.2 79.1 99.5 26.5 CI + F soluble 69.6 60.5 67.4 32.8 73.8 33.1 18.2 67.4 45.1 Unlimed soil (pH 5.3) 103 86 88 65 84 64 37 93 92 Limed soil (pH 7.3) 40 59 77 44 57 55 23 76 50

Z B'df Aa Bl L'th L o Bae Wl Pf

loo
85.2

Finally, the influence of drying on the solubility of sludge phosphate has to be discussed. For practical reasons the sludges used in the solubility experiment and in the pot trials were dried at 105 C. It was observed that due to this heat treatment the solubility in citric acid was reduced by 10 to 30%, and even in some cases by 40% (Hani and Gupta, 1978). As 70% of the total P of most sludges which were analysed in the wet form was in citric acid form, it may be concluded that the P efficiency of wet sludges, as generally used in agriculture, can be compared with that of basic slag. The influence of heat treatment on the CI + F soluble sludge phosphate should also be determined due to the possible over-estimation of plant available phosphate by citric acid. 4. SUMMARY AND CONCLUSIONS Prediction of the efficiency of sludge phosphate was attempted through the use of chemical methods in combination with growth experiments. The two first fractions of the successive extraction technique as proposed by Chang and
187-

Jackson (1957) for the characterisation of soil phosphate were of further interest in the search for plant available phosphate of sludges. These two fractions represent easily exchangeable phosphate (soluble in NH.C1) and phosphate which is either more strongly adsorbed on the surface of iron and aluminium oxides or belongs to the bulk of aluminium components (soluble in NH .F) . The phosphate dissolved in NaOH and H_SO. is of no direct interest regarding plant availability as it is too strongly bound. Because a correlation of r = 0.694 was found between CI + F -and citric acid - soluble phosphate this solvent, i.e. citric acid, could be appropriate for the estimation of plant available sludge phosphate. However, the relatively high solubility of some burned sludges in citric acid may be an indication that there is a danger of possible over-estimation when using this solvent. Until now, apart from thorough chemical investigation, it has only been possible to test 9 sludges in pot trials. From the results it can be seen that the % P utilisation of sludges is correlated by r of 0.94 and 0.87 with the citric acid and Cl + F -soluble phosphate, respectively. For practical reasons, citric acid is proposed to determine the effective phosphate content of sewage sludge. As wet sludges show a solubility which generally exceeds 70% of the total phosphate it is concluded that sludges may be judged in a similar way to basic slag. However, greater knowledge is needed of the mechanism of citric acid dissolution, as in certain sludges (possibly burned and iron-rich ones) it seems that phosphate fractions which give no correlation with plant uptake are attacked.

188-

REFERENCES Bromfield, S.M., 1967. Austr. J. SoilRes. 5 _ , 93. Bromfield, S.M., 1967. Austr. J. SoilRes. 5 _ , 225. Chang, S.C. and Jackson, M.L., 1957. Fractionation of Soil Phosphorus, Soil Sci. 84, 133-144. Fife, C.V., 1959a. Soil Sci. 87_, 13. Fife, C.V., 1959b. Soil Sci. 87_, 83. Gupta, S.K., 1976. Diss. Bern. Gupta, S.K. and Hani, H., 1979. Estimation of Available Phosphate content of Sewage Sludges, Cadarache Symposium COST. Hani, H. and Gupta, S.K., 1978. Kann Klarschlamm als P-Dtlnger verwendet werden? Schweiz. Landw. Forschung 17, 15-28.

DISCUSSION D. Sauerbeck (FRG) I did not quite understand why you neglected the sulphuric acid fraction. There is always a lot of free calcium in sewage sludges and there will be a considerable formation of calcium phosphates which are known to be much more available than the calcium phosphate that you usually obtain by the Chang and Jackson procedure when you fractionate soils. When you compare with the citric acid extract, again, you dissolve most of this calcium bound phosphate. So what is your reason for neglecting this fraction in your comparison? H. Hani (Switzerland)

One reason is that in sewage sludge we also dissolve quite a high amount of calcium phosphate by ammonium chloride. M. Webber (Canada) Are you suggesting that this kind of method would be used to predict the availability of phosphorus in sewage sludges?

189-

H. Hani Yes, we hope to be able to give the farmers a better indication of the amount of phosphate available in sludge. That is our aim but we must have more experiments D. Sauerbeck Can you tell us something about the solubility of phosphorus in ammonium chloride when you compare the different sludges? Is the figure you give, which is amazingly high, an exception or a regular occurrence? H. Hani We have many figures for the phosphate content in the ammonium chloride fraction but not yet for the calcium content. But the figure for phosphate does not seem to be abnormally high compared with other sludges. D. Sauerbeck

But compared t o s o i l s , i t i s an order of magnitude h i g h e r , percentage-wise. H. Hani

yes, that is true, but I think you expect the mobility of phosphate to be higher in sludge than in soil.

190-

PHOSPHORUS PROBLEMS AND SEWAGE SLUDGE APPLICATION IN AGRICULTURE A. Suss Bayerische Landesanstalt fur Bodenkultur und Pflanzenbau, Vttttinger Str. 38, 8050 Freising, Federal Republic of Germany. ABSTRACT Due to the complexity of phosphorus metabolism therefore remains necessary in soil plant of the material, are difficult. influenced rate period of over studies on the availability application and sludge are

from sewage sludge is considerably in sewage sludge available P for a longer any problems

However,

phosphorus

by sewage sludge from sewage Soil analyses

With an increase extractable

the amount of CAL - soluble in soil.

increased. P hosphorus

to avoid

fertilisation.

191

INTRODUCTION Sewage sludge is used in agriculture as a soil conditioner, a source of organic matter and nutrients. As well as nitrogen, phosphorus is becoming more and more important. Calculating the phosphorus content and the amount of sewage sludge applied to agricultural land, 50 to 60 000 tons of P^Cv fertiliser can be recycled. This is about 6% of the P fertiliser used in the FRG. The origin of phosphate in sewage sludge has several sources. The main one is detergents. Our surface water becomes more and more polluted, while phosphorus is in many cases the limiting element. Several factors must be considered in the use of sewage sludge on arable land: 1. 2. 3. The composition of sewage sludge must be continuously controlled by chemical analysis. The nutrient value must be considered for the soil type and the plant species.. The content of heavy metals in soil and sewage sludge must be recorded.

The plant availability of nutrients is determined by several extraction methods. For phosphorus the following classification is used: A B C D E low middle high very high < 11 11 - 18 19 - 35 36-60 > 60 mg/100 g air dried soil

- extremely high

In the FRG about 45% of the cultivated soil belongs to scale A and B, another 20% to C, 15% to D and the rest to E. It is known from plant physiology that a soluble P content
- 192-

higher than 100 mg may be toxic to plants. The phosphorus in sewage sludge is soluble, to a high degree in a CAL-solution. The problem with the use of sewage is to avoid an over fertilisation with phosphorus. EXPERIMENTS AND METHODS Sewage sludge trials were performed in the field as well as in pot experiments, using Kick-Brauckmann pots with 7 kg soil. The field trials were carried out in 4 different locations and soil types. Detailed analyses of the soils have already been published (Suss et al., 1978). The soil and sewage sludge samples were ashed by a wet ashing method and the total element contents were determined (Schmid et al., 1978) . For the soluble phosphorus in soil the LUFA-extraction method was applied. RESULTS The determination of phosphorus availability presents several difficulties, because as with mineral fertiliser trials, one is unable to distinguish between nutrient effect and the influence of minor elements, organic matter and toxic substances. The best comparisons were therefore the phosphorus content of soil and plants and the yield of the test plants. The idea in the experiments was therefore to use application amounts as practised in agriculture. The phosphorus content of sewage sludge varies from 3 - 7 % in dry matter. Looking to the total P content in soil, because a content of about 150 mg/100 g changes can be found only after a long term application. A comparison of the P content of plant material from field trials, even after a high rate of application of sewage sludge, showed no significant increase. When an increase is indicated in maize straw, no variations can be seen in spring wheat and barley.
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TABLE 1 PHOSPHORUS CONTENT ( % ) OF VARIOUS TEST PLANTS AFTER SEWAGE SLUDGE APPLICATION. FIELD EXPERIMENTS 1976-1979; 4 LOCATIONS Plant species m /ha Control 0.42 0.26 3 X 130 0.40 0.23 1 x 400 0.42 0.25 1 x 800 0.42 0.30

Corn Maize straw Spring wheat grain straw Spring barley grain straw

0.37 0.09

0.38 0.09

0.37 0.09

0.37 0.10

0.31 0.06

0.31 0.08

0.31 0.06

0.31 0.08

TABLE 2 PHOSPHORUS EFFICIENCY RELATED TO MINERAL FERTILISER IN FIELD TRIALS, AVERAGES OVER 3 YEARS, 4 LOCATIONS AND 3 TEST PLANTS (CORN, WHEAT, BARLEY), Total yield (dt/ha) 1974 - 1976 Control 3 x 130 m 3 /ha 1 x 400 m 3 /ha 1 x 800 m /ha 1977 - 1979 Control 3 6 x 130 m /ha 2 x 400 m 3 /ha 2 x 800 m 3 /ha 279.3 263.9 218.6 265.0 380 949 872 1 383 lOO
32.8 34.1 20.7
3

P amount (PpO_) (kg/ha)

Efficiency

( % )

243.5 233.3 223.7 257.1

350 1 346 1 465 2 931

loo
24.9 21.9 12.6

- 194-

A more detailed pot experiment with raised amounts of sewage sludge and different levels of plant available water also showed no change in P content of the plants. If we compare the high level of phosphorus in the applications of sewage sludge (250 kg P25 ) with the constant P uptake, we observe an increase of phosphorus in soil. When looking at the results 3 in Table 1,it must be remembered, that 130 m /ha were applied every year, whilst applications of 400 and 800 m /ha were spread as liquid (5% dry matter). The high P application of 800 m /ha gave no change in P uptake. An increase of P availability can be stated only by a higher plant yield (about 120% against a control). The phosphorus effect on plants depends on several influencing factors. In our trials we tried to calculate the efficiency by the total yield. During two crop rotations (corn, wheat and barley) the P efficiency decreased with rising amounts of sewage sludge and P rate. It is interesting to note that the same percentage of P efficiency was found when sewage sludge was applied in low rates (130 m /ha/year) or in one large amount as used with 400 m /ha/3 years. During the first rotation period p-efficiency decreased from 24.9 to 12.6%. In the second period the P efficiency was higher, but this was in accordance with an increased total yield. Furthermore, there were still P sources from the first sewage sludge application, which had to be taken into consideration. It is possible that these phosphates in the soil influence the total yield. The P availability for different locations is shown in Table 3.

195

TABLE 3 PHOSPHORUS EFFICIENCY FROM SEWAGE SLUDGE AT DIFFERENT LOCATION FIELD EXPERIMENTS, 1977-1979, 3 TEST PLANTS (CORN, WHEAT AND BARLEY). Total yield (dt/ha) 3 x 130 m /ha Baumannshof Neuhof Strassfeld Neuriss 1 x 400 m 3 /ha Baumannshof Neuhof Strassfeld Neuriss 1 x 800 m 3 /ha Baumannshof Neuhof Strassfeld Neuriss 258.7 282.6 304.7 213.8 1 645.6 1 656.6 1 600.0 1 503.0 17.7 20.3 23.6 21.6 j 207.5 219.9 257.8 189.1 822.8 828.3 800.3 751.5 28.4 31.5 40.0 38.3 248.8 295.8 302.9 208.1 891.4 891.4 884.0 868.2 31.6 42.0 42.8 35.2 P20,--rate (kg/ha) Efficiency

( % )

The data show the variation according to soil type and location. The figures for Strassfeld and Neuriss show the influence of soil type, because the location (Puch) is the same for both. The distance between these two trials was about 700 m. The efficiency is again related to yield because no changes in P uptake and P content were found. The figures also show that with sewage sludge tremendous amounts of phosphorus appeared in the soil. Analysis of P in soil samples showed that no significant changes could be found for P content between 154 and 210 mg in 100 g soil. Studies of soluble P in soil showed an interesting effect related to the sewage sludge rate.
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TABLE 4 TOTAL YIELD (g/POT AFTER SEWAGE SLUDGE APPLICATION. CONTENTS Plant available water Soil Puch m /ha equivalent Control 177.8 = ICO 50% 191.2 = loo 70% 190.0 = 100 137.4 103.8 110.3 135.0 104.2 108.8 3 x 130 136.0 1 x 400 95.6 1 x 600 104.3 Control 175.4 = 100 190.9 = loo 189.4 = loo 123.8 99.2 105.6 126.4 103.1 111.0 POT EXPERIMENT, 1976 - 1979, IN RELATION TO DIFFERENT WATER

Soil Baumannshof m /ha equivalent 3 x 130 121.5 1 x 400 90.4 1 x 600 94.2

20%

Repeated sewage s .udge application (2 x 600 m /ha) 50% 169.1 = 100

121.9

169.6 = loo

117.0

TABLE 5 CAL-SOLUBLE P (mg/P^/lOO g) AFTER 3 YEARS.- POT EXPERIMENTS.

Plant available water Control 20% 27 = 100 50% 34 = loo 29 = loo

Soil Puch m3/ha equivalent 3 x 130 130 1 x 400 133 1 x 600 163 Control 21 = 100 113 113 140 24 = 100 117 117 141 20 = 100

Soil Baumannshof m /ha equivalent 3 x 130 119 1 x 400 119 1 x 600 171

104

92

125

115

110

150

2 x 3 years == 2 x 600 m /ha equivalent 26 = 100

208

17 = loo

271

Compared to a control which received mineral fertiliser at an average rate, the yield increased after sewage sludge application. The most effective application was a lower rate used every year. The soil type also influenced the yield in relation to sewage sludge. A repeated sewage sludge application brought an increase in yield. The phosphorus values for soil were high and belong to scale C. The influence of plant available water stages has almost no influence on the CAL-soluble amount of P in the control plots. With increasing sewage sludge rates the amount of extractable and plant available P increased. With a water content of 20% plant available water the increase was higher than with 50 and 70% of plant available water. These data indicate, that phosphorus metabolism in soil depends on water availability. A repeated application of sewage sludge has a much more significant influence on P solubility in the soil. DISCUSSION ON THE RESULTS In order to obtain a significant nutrient balance, the applied amounts must be considered in relation to the uptake by plants and the changes in nutrient content of soil (Mengel et al., 1969). Nitrogen and phosphorus are important in the use of sewage sludge, whilst organic matter is important for soil fertility. The P supply of agricultural land in the FRG increased during the last 30 years due to an increase in phosphate rates (Hildebrandt, 1980; Vetter and Frtlchtenicht, 1977). With this experience the higher P level in the soil must be considered when P fertiliser is applied to different plants (Munk, 1980; Munk, 1978). The P availability from P fertiliser was found to be about 50% over a long period of time. The efficiency of P fertiliser has decreased since 1950 because the amount of
199-

soluble P in soil has increased. P fertilisation must be carried out carefully to ensure an economic and ecological use of P. The use of sewage sludge in agriculture can lead to a considerable increase in the amount of plant available phosphorus. The phosphorus from sewage sludge remains extractable for a longer period and it seems that there are in addition interactions with soil phosphates, as a result of which these become more soluble. Considering this fact the efficiency of P-fertiliser is reduced. Sewage sludge application must be carried out with care, because the availability of soil phosphates for plants is influenced by several factors. The use of mineral fertiliser, pH, location factors, soil type, lime fertilisation, water supply, biological activity, humus content and rooting depth must be considered with the use of sewage sludge. The control of phosphorus solubility and content of available P is much more important than the observation of heavy metals in sewage sludge and soil. The last point is considered to be the most important one at present. The phosphorus in sewage sludge remains soluble for a long time and therefore P fertiliser can be saved. It is extremely important to follow continuously the soluble Pcontent of soil by means of soil analysis.

200-

REFERENCES

Hildebrandt, E.A., 1980.

Die Entwicklung der

Nahrstoffversorgung Kali - Briefe, 15,

bundesdeutscher Bflden in den letzten Jahren. 1-14. Mengel, K., Grimme, H. and Nemeth, K., 1969.

Potentielle und effektive

Verftigbarkeit von Pflanzennahrstoffen im Boden Landw. Forschung. 231 I. 79-91. Munk, H., 1978. Zur Frage der PhosphatdOngung im Bereich optimaler bis Forschung, Sonderherft, 35,

hoher Anreicherung des Bodens Landw. 311-324. Munk, H., 1980. 49-62.

P-Dungung auf gut versorgten Bflden Kali - Briefe, 15,

Schmid, G., Rosopulo, A., Stiss, A., Diez, Th., Born, H.J. and Stark, H., 1978. Grundsatzfragen zur Lflsung von Umweltproblemen: Mitt. I:

Untersuchungen fiber die NMhrstoff - und Schadstoffgehalte von verschieden aufbereitetem Klarschlaimn im Hinblick auf die pflanzliche Produktion.Bayr. Landw. Jahrbuch, 55, 878-894. Suss, A., Beck, Th., Borchert, H., Rosopulo, A., Schurmann, G. and Sommer, G., 1978. Ergebnisse 3 jahriger Feldversuche mit

unbehandeltem, pasteurisiertem und Y_i>estrahltem Klarschlamm, Bayr. Landw. Jahrbuch, 55, 481-505. Vetter, H. and Frtlchtenicht, K., 1977. Phosphatdfingerbedarfs. Oldenburg. Untersuchungen zur Ermittlung des

Festschrift 100 jahriges Jubilaum, LUFA -

201

DISCUSSION
H. Tunney (Ireland)

In your Table 2 you refer to phosphorus efficiency. You take the control as 100% and then calculate the different rates from there. I am not too clear exactly how you determine efficiency but it would appear to me that if you apply 350 kg of P in your sewage sludge you would then arrive at a figure of 100% efficiency of phosphorus. A. Suss (FRG) I am talking about relative efficiency; it is not efficiency according to the amount of phosphorus taken up by the plant. It is a relative calculation because the phosphorus content of our plants is not changed by the application of sludge. H. Tunney I think we should be very careful when we are talking about efficiency of phosphorus. It seems to me that your soil is not deficient in phosphorus and you are not getting a P response. So eventually what we are doing with a lot of experiments is just adding extra phosphorus for the future sometimes. Thus, in a sense, when we are talking about efficiency in that regard, I wonder if it makes much difference what the form of the phos phorus is. Suss There was an excess of phosphorus in the soil and we are adding additional phosphorus. I think it is all right if we state that it is relative efficiency compared to mineral ferti liser. H. Tunney I would suggest that it is almost impossible to measure phosphorus in a situation of excess phosphorus.

202-

A Suss It is difficult in our case; we choose soil types where sewage sludge application is used and where we want to see the response. O . J . Fur r e r (Switzerland)

Do you think that 350 kg is enough for maximum yield? Suss Yes, the 350 kg of phosphorus was applied over a period of three years for corn, wheat and barley. This is enough for the place where we made our experiment. O.J. Furrer I am sure that if you applied this amount of phosphate with mineral fertiliser you would have the same decrease of efficiency I would like to emphasise that it would be wrong to say that the efficiency of sludge phosphate is less because of these figures. We have the same results if we apply 3 000 kg, that is eight times more than your 350 kg, giving a comparative efficiency of only oneeighth. Suss Yes, the rate is high but we chose this rate because it was the rate of the location where the experiments were made.
M. Webber (Canada)

Where you applied different rates of sludge, did you main tain a constant level of nitrogen, or did the levels of nitrogen vary with the different rates? A. Suss More nitrogen was applied with the heavy treatments than with the low treatments. However, increase in yield did not correspond to the higher amounts of nitrogen applied.

203-

M. Webber It seems to me though that over the years nitrogen supply could have become limiting and could partly account for the low phosphorus efficiency values. A. Suss It depends on the type of sludge you use. If you use liquid sludge, as we did here, with a dry matter content of 3.5%, this might not be the case but if you used dewatered sludge that would be a different case. D. Sauerbeck (FRG) Referring to your pot experiment, what was the purpose of working with three different moisture regimes, and do these figures 20, 50 and 70 actually indicate 20%, 50% and 70% of maximum water holding capacity? In this case 20% is extraordinarily low. Suss We wanted to see if the water from the sludge had an effect because we had noticed from other experiments that with low amounts of sludge applied every year, the water holding capacity was better. Therefore, we wanted to see the effect of additional water supply. E.G. Coker (UK) Why did you not include a treatment in which you applied the same amount of phosphorus as sludge as you did in the form of mineral fertiliser? You cannot judge the efficiences unless you make that comparison. Suss Yes, I agree, but this experiment was done from the point of view of practical application of the sludge according to the rates recommended to the farmers.

-204-

E.G. Coker I am still worried about the quoted efficiencies; I do not think this is a reasonable conclusion to draw. Suss I agree that if you want the true phosphorus efficiency figures you must have the same amounts of phosphorus in the. mineral fertiliser and the sludge.

205-

PHOSPHORUS EFFECT OF ANIMAL MANURE AND SEWAGE SLUDGE K. E. Larsen Askov Experimental Station, Denmark.
ABSTRACT Results the special year after moderate possible phosphorus from field trials light and lysimeter on the effect types of cattle studies are presented in the and with first beet was

aim of throwing application

of phosphorus uptake between

of various to increasing

manure to barley supply. It has not

on loam and sand soil. in proportion in this

The increase

of phosphorus phosphorus fertiliser.

by the plants the effect of

been

experiment

to show a difference

in animal manure and in with yearly

Experiments phosphorus in sludge from experiments from phosphorus

application

of sewage sludge as phosphorus

indicate

that Results effect

has the same value sludge.

in fertiliser.

with a single in applied value

heavy application

show a good after

The fertilising with Italian uptake ryegrass

of phosphorus crop, of

in chemically tested

precipitated in pot in

sludge

compared with mechanically between the four

precipitated types sludge.

sludge

experiments phosphorus

as a test

showed no difference

Animal manure and sewage sludge P^nutrient cycle.

can make a contribution

to

the

207-

INTRODUCTION For many years it has been more economical to use fertilise] on crops and consequently the interest in the utilisation of organic manure had declined. Animal manure was considered as a troublesome waste product to be disposed of in the easiest and cheapest way possible. The utilisation of organic manure was not financially viable. However, the rise in the price of fertilisers and phosphorus in recent years has put a new perspective on this matter. Animal manure and sewage sludge should be used to the same extent as other fertilisers. CONSUMPTION OF ORGANIC MANURE IN DENMARK Animal manure The total amount devoted to plant nutrients in 19 77/78 was $ 6 24 million, of which $ 376 million was spent on commercial fertiliser and $ 248 million on animal manure, the latter being 40% of the total amount. Nutrient supply in animal manure this year was for nitrogen (N) 29%, for phosphorus (P) 52% and for potassium (K) 54%, of the total application. Therefore, from a fertiliser point of view, animal manure is very important and it must be handled, stored and spread in such a way that the best value of the nutrients will be obtained without causing environmental damage. Because of the differences in quantities and mineral content in the manure from the different species of animal, the value of using animal manure will depend on both the size of stock/area and the composition of stock. Quantities of manure are shown in Table 1 and the mineral content in Table 2.
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TABLE 1 MANURE PRODUCTION FROM DIFFERENT SPECIES OF ANIMAL Quantity, t/year ex dunghill Liquid Slurry FYM manure 8.5 2.5 2.5 2.4 1.1 5.5 2.5 2.5 5.5 16.0

Unit of animal 1 dai ry cow 1 sow 10 pigs lOO hens lOOO chickens x ) xx)

3 young cattle (2 years old) = 1 dairy cow 10 pigs = 3.3 produced baconers/year.

TABLE 2. NUTRIENT CONTENT IN MANURE, kg/t. Description of manure FYM liquid manure slurry FYM liquid manure slurry Hens Broilers

Species of animal Cattle

N 5.9 3.8 4.5 7.5 4.0 6.0 14.0 26.0

P 2.2 0 0.8 3.4 0 1.6 18.0 12.0

K 3.9 6.6 4.0 4.1 2.0 2.7 12.0 17.0

Pig

Poultry

Pig manure has a higher phosphorus content than cattle manure, whilst poultry manure is even higher in phosphorus than either pig or cattle manure. Calculations on the basis of the livestock population of Denmark in 1978 show that, on the average of animal manure available, there will be 15 t/ha as presented in Table 3.

209-

TABLE

MANURE PRODUCTION I N THE DIFFERENT PARTS OF DENMARK AND PHOSPHORUS APPLICATION IN MANURE. ESTIMATE AVERAGE 1 9 7 8 , t / h a .

Area lOOO h a E a s t Denmark Funen Jutland Total x) 622 25 3 20 37 2912

Manure production, t/ha 9.3 13.5 17.0 15.0

P-application i n manure, k g / h a 14.O 18.8 22.7 20.5 district.

S e a l a n d , L o l l a n d , F a l s t e r and Bornholm e x c e p t Copenhagen

The amount of animal manure a v a i l a b l e w i t h i n Denmark i s l a r g e , with 9.3 t / h a i n the e a s t e r n p a r t due to the change i n farming p r a c t i c e to mainly p l a n t - p r o d u c t i o n and 17.1 t / h a i n Jutland where the a g r i c u l t u r e i s based more on animal production. The Danish cows have moved ' w e s t w a r d s ' . Even though the examples c i t e d above show a moderate a p p l i c a t i o n of manure/ha, i t i s n e v e r t h e l e s s necessary to p o i n t out t h a t on many farms with i n t e n s i v e l i v e s t o c k production s u b s t a n t i a l l y higher amounts (50 to 100 t/ha) are used. Table 3 a l s o shows t h a t the average a p p l i c a t i o n of phosphorus in animal manure/ha i s 20.5 kg P / h a / a g r i c u l t u r a l a r e a . The corresponding amount for West Germany i s 15.6 kg P/ha (Vetter, 1977). Sewage sludge The yearly production of sewage sludge from municipal p l a n t s in Denmark in 19 78 was nearly 12 7 000 t dry m a t t e r . Assuming t h a t about 45% of the dry matter produced i s used in a g r i c u l t u r e , the phosphorus content of sludge i s about 2 % of the t o t a l phosphorus (P) consumption in Denmark.

210-

PHOSPHORUS EFFECT Control of the fertilising value of organic manure is complicated because of its diverse effects. The nitrogen effect is clearly shown during experiments but this is not the case with phosphorus. Animal manure Field experiments The relationship between the effect of phosphorus in solid farmyard manure and phosphorus fertiliser can be illustrated from 16 Danish field experiments carried out in the years 19 33 - 38 (Table 4 ) .
TABLE 4 PHOSPHORUS EFFECT OF FARMYARD MANURE AND FERTILISER.

1933 - 38.

AVERAGE 16 EXPERIMENTS

P-supply the f i r s t y e a r for r o o t - c r o p s , kg P/ha Crop 1. y e a r 2. 3. 4. root-crop barley beet barley

Farmyard manure
44 88 44

Fertiliser
88

P i n the f e r t i l i s e r s Additional content in % 14.2 2.1 6.9 0.8 24.0 9.8 12.2 2.5 5.6 0.8 21.1 8.9 14.4 1.0 6.5 0.2 22.1 7.7 11.4 0.9 4.7 0.3 17.3 5.9

Total of 1 - 4 y e a r Total of 2 - 4 y e a r

Farmyard manure and fertiliser were only supplied to the first crop. As can be seen in Table 4, the uptake of phosphorus in the first crop, shown in % supply, was nearly the same for both types of manure. On the basis of this experiment the conclusion was that phosphorus in farmyard manure has the same value as phosphorus in fertilisers (Iversen, 19 38). The following years' uptake of phosphorus was higher after the application of farmyard manure.
-211-

At Askov Experimental Station experiments were established on loam soil in 19 73 and on sandy soil in 19 74 to compare supply and removal of nutrients following the application of substantial amounts of farmyard manure and slurry (D am Kofoed, 1979). Up to 400 t/ha of sludge and cattle manure given every 4th year was compared with applications of up to 100 t/ha given every year and up to 200 t/ha given every 2nd year. The rotation used in two parallel plots was 1. beet, 2. barley, 3. grass and 4. barley. Results from these experiments are given here with the special aim of throwing light on the effect of phosphorus in the first year after application of animal manure. Phosphorus in superphosphate was used as a control. The measured yield, phosphorus content and phosphorus uptake in barley and beet in relation to the farmyard manure and slurry on the loam soil and the sandy soil are shown in Tables 5 and 6. Lysimeter experiments Corresponding experiments have been made in lysimeters. The same soil type was used in field and lysimeter experiments for the sand field, but loam soil used in lysimeters was heavier than loam soil used for field experiments. The levels of yields were higher in the lysimeter experiments because irrigation was possible. Results from the same crops as those used in the field experiments are presented in Tables 7 and 8. As can be seen from the Tables, increasing the fertiliser has only a slight influence on the phosphorus content of the different types of crops, with the largest modification occur ring in straw and beet leaves. The increase of phosphorus taken up by the plants was moderate in proportion to the increasing phosphorus supply.

212-

TABLE 5 APPLICATION OF ANIMAL MANURE FOR BARLEY. LUNDGARD EXPERIMENTAL STATIONS. Fertiliser 2 Slurry, P-supply, kg/ha 19 38.6 25.7 0.37 0.08 13.9 37 48.3 30.8 0.37 0.07 17.0 FIELD EXPERIMENTS, ASKOV AND

Animal m a n u r e , t / h a 100 50 25 loam s o i l 19 44.4 32.6 0.35 0.08 15.5 37 49.4 41.8 0.38 0.09 19.3 loam s o i 1 82 47.0 33.6 0.38 0.13 19.1 16 3 47.9 43.1 0.41 0.17 23.0 74 46.5 49.5 0.36 0.13 19.6

3 expts., 74 44.6 40.7 0.37 0.14 18.8

Yield, dt/ha G r a i n (85% DM) Straw ( - ) P - c o n t e n t , % i n DM Grain Straw P-uptake, kg/ha

Farmyard manure, 3 e x p t s . , P-supply, kg/ha 41 39.7 25.0 0.38 0.08 14.5 82 45.2 35.8 0.37 0.09 16.9 Slurry, P-supply, kg/ha 19 19.1 12.0 0.38 0.06 6.7 37 27.4 20.0 0.31 0.05 8.2 16 3 40.4 44.5 0.41 0.19 21.1 2 expt s . , 73 31.0 32.3 0.37 0.09 12.2 41 38.7 28.1 0.38 0.11 15.2

Yield, dt/ha G r a i n (85% DM) Straw ( ) P - c o n t e n t , % i n DM Grain Straw P-uptake, kg/ha

sandy s o i l 19 19.5 12.4 0.36 0.06 6.6 37 27.2 25.7 0.36 0.08 10.2 s andy 92 27.1 18.7 0.40 0.06 10.3 73 26.7 30.4 0.40 0.13 12.5 soil 182 32.2 28.5 0.46 0.13 15.7

Yield, dt/ha G r a i n (85% DM) Straw ( ) P-content, % in D M Grain Straw P-uptake, kg/ha

Farmyard manure, 3 e x p t s . , P-supply, kg/ha 46 20.4 12.6 0.37 0.05 7.0 92 26.7 16.8 0.32 0.07 8.2 182 29.0 28.7 0.43 0.12 13.6 46 19.6 11.5 0.40 0.07 7.2

Yield, dt/ha G r a i n (85% DM) Straw ( - ) P-content, % in D M Grain Straw P-uptake, kg/ha

213-

TABLE 6 APPLICATION OF ANIMAL MANURE FOR BEET. FIELD EXPERIMENTS, ASKOV AND LUNDGARD EXPERIMENTAL STATIONS.

Fertiliser 2

25

50

Animal manure, t / h a 200 10O

400

S l u r r y , 2 e x p t s , loam s o i l P-supply, kg/ha Yield, DM, d t / h a Root Leaves P-content, % in D M Root Leaves P-uptake, kg/ha
22 44 88 22

44 83.6 38.0 0.18 0.24 24.3

88 96.4 44.7 0.18 0.25 28.6

175

350

89.6 37.2 0.18 0.23 24.3

lo4.7 44.3 0.17 0.23 28.4

115.9 54.1 0.18 0.26 35.2

79.3 35.6 0.19 0.23 23.1

108.0 49.8 0.17 0.26 31.6

110.4 50.2 0.15 0.27 29.9

Farmyard manure, 2 e x p t s . , loam s o i l P-supply, kg/ha Yield, DM, d t / h a Root Leaves P-content, % in D M Root Leaves P-uptake, kg/ha
74 148 295 74

148 74.4 35.6 0.20 0.26 23.8

295 82.6 40.6 0.20 0.28 27.9

590

1180 10O.5 46.3 0.20 0.28 33.1

83.8 35.2 0.19 0.24 24.8

lOO.4 42.7 0.21 0.27 32.2

110.0 52.6 0.23 0.29 40.5

60.6 31.2 0.20 0.25 19.9

94.3 42.4 0.20 0.28 30.8

TABLE 6 (Cont.)

Fertiliser 2

25

50

Animal manure, t / h a 2O0 100

400

Slurry , 2 expts P-supply, kg/ha Yield, DM. d t / h a Root Leaves P - c o n t e n t , % In D M Root Leaves P-uptake, kg/ha
19 38 74 19

i n sandy s o i l 38 101.3 34.4 0.17 0.25 25.5 74 121.9 47.4 0.16 0.27 32.3
148 296

86.6 35.0 0.17 0.24 23.3

91.5 37.9 0.16 0.23 23.0

93.4 42.8 0.17 0.26 26.6

67.0 19.5 0.17 0.24 16.1

125.9 54.7 0.17 0.28 36.9

119.0 57.7 0.18 0.30 38.1

Farmyard manure, 2 e x p t s . , sandy s o i l P-supply, kg/ha Yield, DM, d t / h a Root Leaves P-content, % in D M Root Leaves P-uptake, kg/ha
52 103 206 52

103 79.7 27.3 0.19 0.29 23.3

206 105.6 40.5 0.20 0.29 32.9

412

824

82.1 29.8 0.18 0.24 21.7

91.1 33.5 0.17 0.25 24.1

92.9 44.2 0.18 0.27 28.9

58.9 17.9 0.18 0.27 15.5

125.2 51.4 0.15 0.32 34.9

126.3 58.1 0.20 0.30 42.8

TABLE 7 APPLICATION OF ANIMAL MANURE FOR BARLEY. LYSIMETER EXPERIMENTS, ASKOV.

Fertiliser 2

Animal manure, t / h a 25 50 loo

S l u r r y , 2 expts . , loam s o i l P-supply, kg/ha Yield, d t / h a Grain (85% D M ) Straw ( - ) P-content, % in D M Grain Straw P-uptake, kg/ha
27 53 105

27 59.3 58.7 0.37 0.08 22.8

53 71.0 71.3 0.37 0.10 27.9

105

55.2 54.8 0.37 0.07 20.6

72.2 72.6 0.37 0.06 26.1

88.1 93.7 0.36 0.05 31.0

87.2 89.9 0.37 0.05 31.7

Farmyard manure, 2 e x p t s . , loam s o i l P-supply, kg/ha Yield, d t / h a Grain (85% D M ) Straw ( - ) P-content, % in D M Grain Straw P-uptake, kg/ha
45 90 180

45 57.3 53.3 0.41 0.11 24.7

90 65.3 65.1 0.41 0.10 28.2

180

60.8 55.9 0.37 0.07 22.5

73.4 68.2 0.38 0.06 27.5

89.6 92.1 0.41 0.08 37.6

80.0 78.4 0.43 0.13 38.1

S l u r r y , 2 e x p t s . , sandy s o i l P-supply, kg/ha Yield, d t / h a Grain (85% DM) Straw ( - ) P-content, % in D M Grain Straw P-uptake, kg/ha
27 53 105

27 36.7 30.7 0.36 0.06 12.7

53 49.3 46.8 0 . 34 0.06 16.5

105

37.4 33.8 0.33 0.04 11.4

54.0 52.2 0.33 0.04 16.9

66.9 61.5 0.33 0.05 21.5

57.5 62.3 0.35 0.06 20.5

It has not been possible in these experiments to show the difference in the effect of phosphorus in animal manure and fertilise: The experiments were carried out on soils with the following phosphorus contents: Ft = 6.6 loam soil, Ft = 5.5 to 6.0; sand soil, (P-index, Ft = 3 mg/100 g soil).

216-

TABLE 8 APPLICATION OF ANIMAL MANURE FOR BEET. LYSIMETER EXPERIMENT, ASKOV. A n i m a l manure 4 Slurry, P-supply, kg/ha 22 170.2 65.5 0.20 0.31 kg/ha 54.3 45 172.9 76.0 0.20 0.32 58.9 89 208.1 108.1 0.21 0.29 75.1 Yield, dt/ha Root Leaves P-content, Root Leaves P-uptake, % in D M 0.21 0.31 56.3 0.19 0.29 55.3 0.20 0.30 73.4 loam s o i l 156 194.7 82.8 0.21 0.32 66.7 312 229.8 105.0 0.21 0.32 82.9 6 24 273.3 140.1 0.22 0.32 105.0 0.19 0.30 89.2 0.20 0.34 116.5 25 50 100 200 400

Fertiliser 1 2

1 e x p t , loam s o i l 22 45 185.0 66.5 89 219.9 94.3 178 254.7 134.3 356 273.3 181.9

164.3 70.2

Farmyard manure, 1 e x p t . , P-supply, kg/ha 39 207.6 70.9 0.20 0.31 63.5 78 185.2 92.6 0.23 0.32 72.2 156 222.8 112.5 0.20 0.33 81.7 39 200.8 68.2 0.20 0.30 60.6 78 193.7 78.8 Yield, dt/ha Root Leaves P-content, % in D M Root Leaves P-uptake, kg/ha

0.20 0.31 63.5

Continued.

TABLE 8 (Cont.)

Fertiliser
1

Animal manure 4
25 50 100 200 400

S l u r r y , 1 expt . , sandy s o i l P-supply, kg/ha Yield, d t / h a Root Leaves P-content, % in D M Root Leaves P-uptake, kg/ha
22

45 148.8 51.9 0.18 0.24 39.2

89 164.7 72.7 0.17 0.27 47.6

22

45

89

178

356

91.1 35.4 0.18 0.26 25.6

115.6 34.0 0.18 0.23 28.6

161.3 51.9 0.18 0.24 41.7

206.7 72.6 0.18 0.26 56.1

257.5 84.8 0.18 0.25 67.8

273.3 152.4 0.17 0.26 86.1

P-uotake per cent of supplied

l o o

5o -

5 o

l 5 o

25o

35o P-suoDly. kg/ha Slurry

* Fertilizer

D Solid FYM

Fig.

1:

Relationship between phosphorus supply and uptake, % of supplied.

-219-

The relationship between phosphorus supplied and removed in the aforementioned experiments is shown in Figure 1. Utilisation of phosphorus decreases with increased application of phosphorus, whether phosphorus is supplied in animal manure or in fertiliser. Sewage sludge Field experiments Since 19 74 experiments with a yearly application of 10 and 30 t dry matter in sludge have been carried out at Askov Experimental Station. Two types of sludge with low and high heavy metal content were tested by being applied to different crops on loam, sandy loam and sand soil. Nitrogen and phosphorus in fertiliser were used as a control. The yearly phosphorus supply from sludge and fertiliser to barley and beet is shown in Table 9.
TABLE 9 P-SUPPLY IN SEWAGE SLUDGE AND FERTILISER, kg/ha/YEAR IN FIELD EXPERIMENT WITH YEARLY APPLICATION OF SEWAGE SLUDGE. AVERAGE 1974 - 1 9 7 7 . Treatment crop Barley Beet Control 0 0 Sludge I 186 558 Sludge II 229 687 Fertiliser 32 62

x Sludge I = Sludge with low metal c o n t e n t Sludge I I = Sludge with high metal c o n t e n t Results for y i e l d , 10. value from t h e a p p l i c a t i o n low m e t a l of sludge calon phosphorus c o n t e n t and p h o s p h o r u s uptake

a r e shown i n T a b l e The h i g h e s t is

fertilising

found i n c r o p s w i t h a l o n g growing s e a s o n , Sludge with on a l l in crops.

such as b e e t ,

c u l a t e d on a d r y m a t t e r b a s i s . has a b e t t e r e f f e c t a better nitrogen effect

content 1979).

T h i s r e s u l t may b e b a s e d (Damgaard-Larsen,

the sludge
-220-

TABLE 10 YIELD, P-CONTENT, P-UPTAKE IN BARLEY AND BEET, AFTER YEARLY APPLICATION OP SEWAGE SLUDGE ON LOAM, SANDY LOAM AND SAND SOIL. AVERAGE FIELD EXPERIMENT 1974 - 7 7 . Control I Grain Barley Loam soil Sandy loam soil Sand soil Loam soil Sandy loam soil Sand soil Loam soil Sandy loam soil Sand soil 35 .O 17.9 17.2 0.34 0.30 0.38 10.1 4.6 5.6 54 .5 35 .3 41 .9 0 .30 0 39 0 41 13 9 11 7 14 5 41.2 36.4 36.6 0.34 0.35 0.40 12.0 10.7 12.5 60.9 38.0 41.8 0.27 0.34 0.32 P-uptake, 14.2 11.0 11.5 16.3 14.0 10.2 37.6 28.6 36.4 25.0 22.9 24.8 44.1 29.3 35.0 .07 09 10 Sludge II dt/ha (85% D M ) Fertiliser Control I Straw Sludge II Fertiliser

% P i n dry m a t t e r 0.06 0.08 0.12 kg/ha 0.9 1.0 1.1 2.3 3.1 3.7 0.05 0.13 0.12 .06 .08 ,11

x Sludge I = Sludge with low metal c o n t e n t Sludge I I = Sludge with high metal c o n t e n t

TABLE 10 (cont.)

Control I Beet Loam soil Sandy loam soil Sand soil Loam soil Sandy loam soil Sand soil Loam soil Sandy loam soil Sand soil 70.7 47.8 35.6 0.18 0.17 0.18 12.8 8.3 6.3 124.5 100.6 81.3

Sludge II Root

Fertiliser

Control I

Sludge II Top

Fertiliser

Dry matter, dt/ha 106.6 96.5 67.0 0.18 0.20 0.23 18.7 19.6 15.3 121.8 86.8 91.0 0.13 0.19 0.18 16.4 16.1 16.1 19.6 14.6 14.5 0.22 0.23 0.22 4.2 3.3 3.2 48.5 45.1 41.8 0.25 0.25 0.27 12.2 11.5 11.1 34.0 32.7 24.9 0.24 0.26 0.28 8.3 8.4 7.0 53.7 42.4 43.1 0.24 0.26 0.23 13.0 11.0 9.8

%P in dry matter 0.17 0.20 0.20 20.6 20.2 16.2

P-uptake, kg/ha

x Sludge I = Sludge with low metal content Sludge II = Sludge with high metal content

The phosphorus content of crops is generally nearly the same in spite of the great difference in the amount of phosphorus supplied by sludge and fertiliser, and the variation in phos phorus taken up by the plants is caused by increasing yields. The conclusion of this experiment suggests that phosphorus in sewage sludge has the same value as phosphorus in fertilisers. In 1973 experiments with single heavy applications of two types of sewage sludge were carried out at Askov on sandy loam soil and sand soil to investigate the availability of heavy metal for a number of years (D amgaardLarsen, 1979). To obtain the same yield level in all treatments,nitrogen, phosphorus and potassium were given as a base dressing in the following years. Phosphorus applied in sludge in 1973 and phosphorus supply in fertiliser in the years 19 74 19 78 to barley, beet and grass are shown at the top of Table 11. The phosphorus uptake in the year for application of sludge (1973) was nearly the same from sludge and fertiliser, although sludge gave about 10 times as much phosphorus as fertiliser (middle of Table 11). Levels of phosphorus uptake in the following years (19 74 1978) show 11 18% more uptake of phosphorus after application of sludge compared with fertiliser (the lowest part of Table 11). The results from this experiment indicate that there has been a good after effect from phosphorus in applied, sludge. Phosphorus in municipal waste is one of the most important factors causing eutrophication in water. It can be removed by chemical precipitation, using chemicals such as ferric chloride, aluminium sulphate or calcium oxide. It is possible that chem ically precipitated sludge has other effects in relation to phosphorus on crops because of the additional precipitated chemicals which it contains.

223-

TABLE 11 P-SUPPLY AND P-UPTAKE AFTER SINGLE APPLICATION OF SEWAGE SLUDGE. OF BARLEY, BEET AND GRASS CROP EVERY YEAR. Sludge low high metal content P-supply, kg/ha 1973 (start year) Barley Beetl and grass 1974 - 78 (every year) Barley Beet and grass 26 2 524 16 28 384 768 16 28 31 62 16 28 | AVERAGE

Fertiliser

P-uptake, kg/ha (accumulated) 1973 1974 1975 19 76 1977 1978 21 43 63 79 94 114 21 44 64 81 98 119 22 39 55 69 84 103

Levels of phosphorus (Fertiliser treatment = 100) 1973 1974 19 75 19 76 1977 19 78 97 112 115 114 112 111 97 114 116 118 117 116

loo
100 100 100 100 100

Pot experiments The fertilising value of phosphorus in chemically precipitated sludge compared to that of mechanically precipitated sludge was tested in pot experiments at Askov Experimental Station in 19 75 and 19 76 with Italian ryegrass as a test crop on sand soil with different pH levels and sandy loam soil. Sludge was applied in 1975 and the residual effect was measured in the following year. The chemical composition of the sludge is shown in Table 12.
224-

TABLE

12

ANALYSES OF SLUDGE, I N % DRY MATTER.

D M

Sand

%
Me c h a n i c a l l y - p r e c i p i t a t e d Al-precipitated CaFe19.1 37.7 40.8 58.3 9.8 17.4 11.4 20.3

P K N % i n dry m a t t e r 1.67 3.00 0.53 1.96 0.99 2.58 0.65 1.88 0.06 0.09 0.02 0.09

x = in acid insoluble ash I n Table 13 t h e p h o s p h o r u s c o n t e n t of t h e crop i n b o t h e x p e r i m e n t a l y e a r s i s shown.

TABLE 13 P-CONTENT, %P IN DRY MATTER OF ITALIAN RYEGRASS. 1975 AND 1976. Sand s o i l pH s c a l e Year Control Sludge: Mech.-precipitated AlCaFeFertiliser Superphosphate 5.0--5.5 1975 0.30 0.36 0.35 0.31 0.32 0.31 1976 0.22 0.25 0.25 0.26 0.23 0.24 6.5-7.0 1975 0.27 0 . 31 0.31 0.29 0.30 0.28 1976 0.18 0.21 0.21 0.22 0.20 0.20 8.0--8.5 1975 0.30 0.30 0.28 0.29 0.29 0.29 1976 0.19 0.22 0.21 0.20 0.21 0.23 POT EXPERIMENT ASKOV,

Loam s o i l 6.5 -7.0 19 75 0.27 0.26 0.27 0.29 0.27 0.29 1976 0.24 0.26 0.25 0.25 0.25 0.24

The results show that, under these experimental conditions, there was no difference in phosphorus uptake between the four types of sludge and superphosphate. The results correspond to Swedish research by Jansson (1970) From these two examples one can conclude that, in general, chem-icals used in precipitation have no influence on phosphorus availability.
- 225 -

THE PHOSPHORUS STATUS IN SOIL. The basis for fertilising with phosphorus from an economic point of view is knowledge of the amount of phosphorus in the soil. Over the years many experiments have been carried out to determine suitability of soil analysis. Different routine methods are used and they have their advantages but also their limitations. Figure 2 shows the results of the extraction of phosphate from the soil compared to the addition of phosphorus with increased application of sewage sludge. The investigation is based upon the aforementioned field experiments. The analytical method in question is the sulphuric acid method (Ft, P-index = 3 mg P/100 g soil). In relation to the supplied quantity, the increase of phosphorus in the soil (Ft) is revealed only on a modest scale by this analytical method. The same results were found with other methods such as the cation-exchange method (Fot) and the anion-exchange resin method (P-resin).

CONCLUSION As a result of the rise in price of phosphorus in fertiliser the interest in the utilisation of phosphorus in organic manure is growing. Animal manure and sewage sludge can make a contribution to the P-nutrient cycle. Many questions in relation to phosphorus in organic matter require further research and experimental work must therefore be continued.

226-

Ft (3 mg P/loo g soil)

15 13

o
x Loam s o i l o Sandy loam s o i l

2oo

4oo

6oo

Ooo

looo

12oo

14oo

16oo

18oo

2ooo

kg P/ha in sludge F i g . 2: Determination of t h e P - s t a t e i n s o i l . The amount of P e x t r a c t a b l e i n 0.2 n 8 SO (the F t value)

REFERENCES o

Damgaard-Larsen, S . , Larsen, K.E. and Spndergaard Klausen, P . t i l f ^ r s e l af slam fra rensningsanlaeg t i l l a n d b r u g s j o r d . for P l a n t e a v l 83_, 349-386 Damgaard-Larsen, S . , Larsen, K.E. and S^ndergaard Klausen, P . s k r i f t for P l a n t e a v l 3 , 387-403 I v e r s e n , K. 1938. Fosforsyre og kalifors?Sg 1927 - 34.

1979.

Arlig

Tidsskrift 1979. Tids-

Engangstilf?(rsel af slam fra r e n s n i n g s a n l a e g t i l landbrugs j o r d . Tidsskrift for

P l a n t e a v l 4_3, 369-459 Jansson, Sv.L. 1970. GfldlingsfdJrso'k med kemisk f a l l d a s l a m t y p e r . 1979. Hygienisk revy 59 (8), 350-356 Dam Kofoed, A. and Nemming, 0 . animal manure to l a n d . V e t t e r , H. and Frtlchtenicht, K. Phosphatdungerbedarfs. Seminar, Bad Zwischenahn. Experiments on heavy a p p l i c a t i o n s of EEC I n : E f f l u e n t s from Livestock, P r o c . 1977. Festschr.

Applied Science P u b l i s h e r s , 184-217. Untersuchungen zur Ermittlung des 100 j3hr Jubilaum Lufa Oldenburg

-228-

DISCUSSION A.E. Johnston (UK) I am sorry not to have followed what you mean by your anal ytical method. You use Ft, presumably to signify that you are extracting the soil with sulphuric acid, but what does the 'Pindex = 3 mg P/100 g soil1 mean when you then have a scale which is plotted from 0 to 17? Is 3 the base line is that the lowest level you would expect? K.E. Larsen (Denmark) 3 mg P/100 g soil is the same as 75 kg P/ha. P. Sauerbeck (FRG) With regard to your soil test data, can you give us an idea of the limits for low, medium and high contents of phosphorus in soil? A. Dam Kofoed (Denmark) May I come in here? As far as this index is concerned, we are a little bit sorry that we use this special scale for phos phorus control in the soil in Denmark. It goes back to the 19 20s, but it would be better to have a Pindex of about 6 to 8. It is very important to have a standard method for measuring phosphorus effect. Some people talk about the relationship between uptake and removal; some talk about phosphorus content after application of superphosphate, slurry phosphorus and sew age sludge phosphorus. There are different ways to try to analyse this question. Even this afternoon some of the data presented have shown how difficult it is to change the P content of the crops significantly. So, there is a problem here, what is the best method to use when we talk about efficiency of phosphorus in field trials.

229-

H. Vetter (FRG) I think your excellent experiments have shown that the efficiency of phosphorus in slurry, or sewage sludge, can only be measured by applying low rates. Do you think that in practice only small applications of sewage sludge should be used or is this not practical? K.E. Larsen (Denmark) It would never be higher than 50 t dry matter because in Denmark we have very strict regulations and cadmium is the limiting factor. There have been extensive discussions between the authorities and the research workers. Formerly, the limit for cadmium was 15 g/ha. We wanted to have it raised to 50 g/ha because no farmer will want to take sludge if he is only permitted to apply 1, 2 or 3 t DM/ha. If the limit was 50 g/ha then it would mean a maximum application rate of between 12 and 15 t DM/ha. This would encourage the farmers to use the sludge and that would be a benefit to the community as a whole. A. Cottenie (Belgium) In your paper you say, "With regard to phosphorus, the content in crops is generally nearly the same in spite of the great difference in phosphorus supply between sludge and fertiliser ". I agree with you; it is also our experience. You also say that the phosphorus taken up by plants is caused by increasing yields. Yesterday, Dr. de Haan showed us his experiments with trees in pots. If I remember correctly, he said that there was a very big difference in content in the leaves of his trees. Is there not some contradiction here? How can you explain this? A. Dam Kofoed (Denmark) This is an important question because people who are concerned with animal husbandry and animal feedstuffs ask us whether it is possible to use more phosphoric acid phosphorus to improve

-230-

quality. Perhaps Dr. de Haan can offer an explanation for the difference.
S. de Haan (Netherlands)

I am afraid that I cannot explain the difference. With ryegrass there was certainly a very good effect of phosphate concentration in the crop in many experiments. But I do not know why it is different in other plants. In my opinion we should first eliminate the nitrogen effect if we want to compare phosphate fertiliser with superphosphate. A. Cottenie Indeed, it was in your nitrogen/phosphorus experiment I heard the expression 'luxury consumption of phosphorus' for the first time. We used to use this expression for potassium but never for phosphorus. Luxury consumption is when the concentration in the plant increases without an increase in yield. This is what you observed. There is a fundamental contradiction in what we observed and I cannot explain the reasons for it. S. de Haan I have no explanation either. We must do further research and make comparisons on the same basis. E.G. Coker (UK) I would agree with Dr. de Haan that the nitrogen should be kept uniform. With regard to the question that has been asked by Professor Cottenie, I just wonder whether there might be anything in an observation which I have made that where the phosphorus level in the soil is, in general terms, reasonably high, we have found very little effect on phosphorus level of adding phosphorus in sludge. However, where we have been operating on a soil with very low phosphate, we have shown clear differences in phosphorus level in ryegrass from the second year onwards.

231

S. de Haan The soil we used was very deficient in phosphate; it is difficult to find a phosphate deficient soil but this one had a very low concentration of available phosphorus. Maybe on a normal soil it is not possible to show an increase. A. Dam Kofoed This is a very important question. There was a publication from East Germany which dealt with the effect of phosphorus in slurry. It was a pot experiment on almost pure sand. It was a very interesting experiment.

232-

SESSION

IV

ACCUMULATION AND TRANSPORT OF PHOSPHORUS

AFTER

LANDSPREADING OF SL UDGES AND SL URRIES

Chairman: A. C o t t e n i e

2 3 3 -

ACCUMULATION AND LEACHING OF PHOSPHORUS AS INFLUENCED BY SLUDGE APPLICATION O.J. Furrer Swiss Federal Research Station for Agricultural Chemistry, and Hygiene of Environment, CH-3097 Liebefeld-Berne, Switzerland. ABSTRACT Because sewage sludges P-overfertilisation. Results have a high. P-content, of a lysimeter was applied there shows: by the crop, is a danger of 4 years

experiment

during

where a dose of 12 t DM sludge/ha/year - a P-input 4 times higher

than the P-uptake soil.

- a P-aaoumulation - an increase - no increase During 4 years field experiment.

of 800 kg in the top content

of the soil in

of soluble

P from 2.9 to 11.8 ppm,

P-leaching. was applied in a

a dose of 480 m sludge/ha/year are as follows:

The results

- a P-accumulation - an increase of two, - an increase

of 2 000 kg P/ha in the P-content

soil, layer by a factor

in total

in the surface

in soluble

P by a factor

of

ten.

-235

INTRODUCTION pH of most of the soils in Switzerland lies between 5 and 7.5. In addition, the soils contain considerable amounts of clay and organic matter. The P-adsorption capacities of these soils are very high. As a consequence, a pronounced accumulation of phosphorus takes place in the uppermost soil layer close to the surface. On the other hand the movement of phosphorus through the soil profile is extremely slow and consequently the leaching of phosphorus applied on the soil surface is very low. That is true for acidic soils consisting of pure quartz sand or pure organic matter. RESULTS OF A LYSIMETER EXPERIMENT The effect of sewage sludge and compost was tested from 1974 to 1978 in an experiment (Furrer, 1979) with lysimeters (080 cm, depth 90 cm), filled with soil with the following characteristics: pH (H20) = 6.2, clay = 18%, C = 2.4%. The following fertiliser treatments were tested (in brackets: application amounts of N, P and K, kg/ha per year):
0 Miner SS SS RC 4 8 8 = control, no fertilisation = mineral fertilisation = sewage sludge = sewage sludge = sewage sludge = town refuse compost = town refuse compost = town refuse compost (N-P-K= 0 0 91 0) 15) 31) 46) 10) 21) 31)

(N-P-K= 250 4 t DM (N-P-K= 236 -

50 - 300)

8 t DM (N-P-K= 471 - 182 12 t DM (N-P-K= 707 - 273 8 t DM (N-P-K= 56 17 34 52 18 t DM (N-P-K= 113 24 t DM (N-P-K= 169 -

SS - 12 RC - 16 RC - 24

All eight treatments were tested in two replications with grass. In addition the treatments '0', 'miner' and 'RC - 16' were tested in bare (unplanted) lysimeters.

-236-

TABLE 1 YIELD OF GRASS (t DM/ha per year) DRAINAGE WATER (mm per year) AND EVAPOTRANSPIRATION (mm per year, 1/kg DM) PRECIPITATION: 986 mm per year Yield t DM/ha 6.4 15.3 4 8 10.8 14.4 18.4 8.4 7.4 9 Drainage water mm 459 313 375 316 272 402 416 381 632 633 639 Evapotranspiration mm 1/kg DM 527 313 611 670 714 584 570 605 354 353 347 825 673 568 477 363 699 772 674

Treatment 0 Miner SS SS -

SS - 12 RC 8

RC - 16 RC - 24 0 Miner RC - 16

TABLE 2 P-BALANCE (kg P/ha per year) . IMPORTS: FERTILISERS, WASTES, PRECIPITATION, EXPORTS: UPTAKE BY CROPS, LEACHING Imports Fertilis. Grass 0 miner SS SS 4 8 0 50 91 182 273 17 34 52 0 50 34 Precipit. 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Exports Crop 36 55 53 65 72 39 35 40 Leaching 0.4 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5 + + Balance (Imp.-Exp.)

Crop treatment

36 5 38

+ 117 + 201

SS - 16 RC 8

RC - 16 RC - 24 Bare 0 miner RC - 16

22 1 12

50 34

-237-

TABLE 3 P-ACCUMULATION IN THE SOIL: P-CONTENT AT THE BEGINNING (1973) AND AT THE END (1977) OF THE TRIAL (ppm and kg P/ha). CHANGES IN P-CONTENTS DURING THE TRIAL (A, kgP/ha). P-ACCUMULATION DETERMINED AND CALCULATED (BALANCE FROM TABLE 2) IN kg/ha FOR A PERIOD OF 4 YEARS Soil layer ppm 1973 1977 0 miner SS 4 SS - 12 984 956 990 1 038 1 233 0 - 25 cm kg/ha 3 130 3 040 3 150 3 300 3 920 25 - 50 cm P-accumu lation

A -90 +20 +170 +790

ppm 702 691 682 697 711

kg/ha 2 420 2 380 2 350 2 400 2 450

A -40 -70 -20 +30

Determ.

Calcul.

-130 -50 +150 +820

-144 -20 +152 +804

Table 1 shows the yields, the evapotranspirations and the amounts of drainage water for each treatment. Table 2 contains the P-balance. With sewage sludge, high amounts of P are applied causing an overfertilisation of 38 to 201 kg P/ha/ year. The amount of P in precipitation is higher than the amount of P in the drainage water. The P-content of both, precipitation and drainage water lies between 50 and 100 mg P/m . The P-accumulation takes place only in the top layer of the soil (Table 3 ) . The increase of the soluble P-fraction is more pronounced in the top layer of the soil (Table 4).
TABLE 4 THE CONTENT OF SOLUBLE P IN THE SOIL: SOLUBLE IN C02-SATURATED WATER (W PPM);

SOLUBLE IN Ca-LACTATE (CAL mg/100 g);

Soil layer (cm) W ppm 0 miner SS - 12 0 miner SS - 12 0 miner SS - 12 0-10 2.9 8.4 11.8 17 31 42 13 25 36

SOLUBLE IN DOUBLE-LACTATE (DL mg/foO g) ,

10 - 25 1.5 1.4 2.0 14 13 16 11 10 14 25 - 50 0.3 0.3 0.3 6 6 6 3 3 3 50 - loo 0.3 0.3 0.3 6 6 6 3 3 3

Cal mg/lOO g

DL mg/100 g

-238-

RESULTS OF A FIELD EXPERIMENT The effect of spreading rates (120 and 480 m /ha/year) of sewage sludge (SS) and pig slurry (PS) were tested from 1971 to 1975 in a field trial (Furrer, 1977) on a heavy soil (61% clay, pH 7.2).
TABLE 5 P-BALANCE FOR A PERIOD OF 4 YEARS (kg P/ha) AND COj-SATURATED WATER," SOLUBLE P-CONTENT (ppm) OF SOIL Treatment Import: mineral fertiliser organic wastes Export: uptake by crops P-accumulation Soil (0 - 15 cm) soluble P ppm 1.4 2.6 10.4 1.7 7.0 212 +88 220 +436 268 +2 068 236 +168 280 +1 112 300 miner SS - 120 SS - 480 PS - 120 PS - 480

656

2 336

404

1 392

In a period of only 4 years a P-accumulation of more than 2 t P/ha (almost 5 t P25^ w a s foun< ^ (Table 5) , due to the higher rate of sewage sludge (SS - 480). The total P-content of the top (0 - 15 cm) layer of the soil was more than doubled (original content: 1.9 t P) and the soluble P-content (Table 5) increased by a factor of ten (soluble P at the beginning = 1.0 ppm). Sewage sludge is often reported as an important source of organic matter. But in order to add 10 tonnes of organic matter per ha, about 1 000 kg of P would have to be applied, which is enough for the need of plants for a period of 30 years. The ratios of organic matter to phosphorus (OM/P) for different organic fertilisers are as follows:

-239-

Peat Straw Farmyard manure

: OM/P = 3 OOO : OM/P = : OM/P = 800 170 10.

Sludges (with P-elimination): OM/P =

REFERENCES Furrer, O.J., 1977. Einfluss hoher Gaben an KlMrschlamm und Schweinegulle Landw. Forschung.

auf Pflanzenertrag und Bodeneigenschaften. Sonderheft 33/1, 249-256. Furrer, O.J., 1979.

Die Wirkung von Klarschlamm und Mflllkompost auf Bulletin

Pflanzen, Boden und Sickerwasser in einem Lysimeterversuch. Bodenkl. Ges. Schweiz. 3, 73-82.

DISCUSSION D. Sauerbeck (FRG) Are there any estimations in Switzerland of the percentage contribution to surface water pollution from soil erosion? O.J. Furrer (Switzerland)

We have made such estimations. The result was less than 10%. That is a general average calculation. There is considerable variation between densely populated catchment areas and primarily agricultural areas.

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EFFECT OF PHOSPHORUS IN SEWAGE SLUDGE ON PHOSPHORUS IN CROPS AND DRAINAGE WATER S. de Haan Institute for Soil Fertility, Haren (Gr.), The Netherlands.
ABSTRACT From two previously the other precipitation six year period so as to produce air-dried sewage sludges, content, by leaching water equivalent pointing especially one with to the a low and intervals, in a mobility with annual removal

with a high heavy metal surplus

in monthly

an amount of drainage in the Netherlands under these content. air-dried

(300 mm), phosphorus

was 0.25 and 0.06% respectively, conditions,

to a low

of P in sewage sludge the high heavy metal

in the sludge

From six previously substrates, order, times) except this soil except more mobile. P removal

sewage sludges,

used as

plant

by leaching

in a seven year period water was more or less on the sludge

was of the same acid and P was much (4 - 20 were high, sludge Mixing or a crops, P in of clay

when the drainage In general,

P removal by crops was much greater Crop yields contents reduction substrates and mobility waste waters) in the mixture, were high.

than by leaching. when heavy metal resulted resulted in a strong

For one

in crop growth and P uptake. with a sandy soil P taken uptake up by of sludge of sludge

one of the sludges although sludge even with (less

(from domestic only 5% sludge year).

in an increased

percentage

a seven year period

was no more than 8 - 10% of the initial

amount of P in

than 1.5% per

Uptake of P from liquid amounts ranging grassland, sludge values yield applied. for arable effects,

sludges, arable

applied DM/ha/year, land,

every

year since

1972 in

from 7% to 22% tons. For the sludge owing almost P an uptake sludge was with

varied

from 15 to 10% for on the amount of however, of in this of negative sludge. phosphorus

and from 21 to 14% for

depending years

high heavy metal

content,

land were lower in the last certainly observed.

-241 -

because

to the heavy metals No leaching

For fertiliser from the liquid

of 20% was assumed.

INTRODUCTION Besides experiments aimed directly at the evaluation of sewage sludge as phosphate fertiliser (De Haan, this seminar), there are a number of more comprehensive experiments at our institute in which various aspects of the utilisation of sewage sludge as organic fertiliser, soil amendment or substrate for plant growth,have been studied. These experiments provided additional data about plant availability and leachability of phosphate in sewage sludge, which will be presented in this paper. The experiments are discussed separately below. 1. EXPERIMENT WITH TWO SEWAGE SLUDGES, LEACHED AT MONTHLY INTERVALS, AFTER HAVING BEEN AIR-DRIED IN 1973, TO STUDY THE CHANGES IN THE CHEMICAL COMPOSITION OF THE DRAINAGE WATER IN THE COURSE OF TIME For this experiment, 140 litre vessels were used with a 2 surface area of 0.2 m and a depth of 0.7 m. Just above the bottom of the vessel there was an outlet for the drainage water and on the bottom a 5 cm gravel layer, covered by a nylon sheet, on which the sludge was placed. Before being put into the vessels, the sludges had been on drying fields for about three months, followed by air-drying and shredding. One of the sludges (Leeuwarden) had a low, the other (Heerenveen) a high heavy metal content. The P contents (as P25^ w e r e 5.00 and 6.23%, respectively, corresponding to about 143 000 and 178 000 kg/ha, respectively. Every month the sludges were given enough demineralised water, to allow collection of about 5 litres of drainage water per vessel per month, resulting in an annual amount equal to the mean precipitation surplus in the Netherlands (300 mm). The drainage water was analysed monthly for pH, COD and EC, and every three months also for macro- and micro-elements.

242-

The P concentrations in the drainage water have been plotted against time of collection in Figure 1. Concentrations drop from a rather high level in the first years to a rather low level in recent years. The level was lower for Heerenveen, notwithstanding a higher P content of the sludge.

phosphorus in drainagewater mg P 2 0 5 /liter

1973

1974

1975

1976

1977

1978

1979

F i g . 1.

Concentrations of phosphorus in drainage water from p r e v i o u s l y a i r - d r i e d sewage sludge in t h e course of t i m e .

Cumulative amounts of P in the drainage water on a h e c t a r e b a s i s are presented in Figure 2. In the period June 1973 - December 1978 about 400 kg P^O^/ha was leached from t h e sludge from Leeuwarden and about 100 kg/ha from the sludge from Heerenveen, being about 0.25 and 0.06%, r e s p e c t i v e l y , of the o r i g i n a l amount of P in t h e sludges. Corresponding figures for nitrogen in the sludges were 13 and 5%, r e s p e c t i v e l y (De Haan, 1980). This p o i n t s t o a low mobility of P in sewage sludge compared with N.
-243-

phosphorus in drainagewater (kg P 2 0 5 /ha) 400 r

rden 300

200

1973

1974

1975

1976

1977

1978 1979

Fig. 2.

Cumulative amounts of phosphorus in drainage water from previously air-dried sewage sludges.

The pattern of release for P from the two sludges is rather similar to that for N; with regard to N, the lower mobility of P in the Heerenveen sludge might be due to a lower decomposition rate of the organic matter in this sludge, and this again could be related to the higher heavy metal content of this sludge. In the next experiment we will see that an acid reaction of the drainage water from the sludge was accompanied by a high mobility of the sludge-P, but this could not be the reason for a higher mobility of P in the Leeuwarden sludge, because pH values of the drainage water for this sludge, as for the Heerenveen sludge, have been > 7 up to now.

244-

2. EXPERIMENT WITH SIX AIR-DRIED SEWAGE SLUDGES AS PLANT SUBSTRATES This experiment has been in progress since 1972 and is carried out in the same way as the previous one, with the exception that now crops are grown on the substrates. The crops were: 1972 mustard, 1973 grass (six cuts), 1974 maize, 1975 sugar beet, 1976 potatoes, 1977 in succesion spinach, dwarf beans and radish and 197 8 in succesion lettuce and celery. Crops have been analysed for macro- and micro-elements, except for the grains of mustard in 1972 and the straw of the beans and the leaves of the radish in 1977. The contents of P in these parts of the crop have been estimated on the basis of the best available knowledge. The drainage water has been analysed for the same characteristics as in the first experiment, once or twice a year, except in 197 4, when no analyses were made. Values for this year have been estimated as intermediate between 1973 and 1975. As the sludges were part of an experiment with normal soils, they were supplied with mineral fertilisers as these soils were, though in the first years a reduction was made for N and P in the sludges. In the 1972/78 period, mineral P was supplied on the basis of 830 kg P25 per hectare in addition to amounts of 164 000, 56 150, 149 000, 79 100, 148 500 and 134 300 kg/ha in the sludges, which were from the towns of Leeuwarden, Apeldoorn, Leiden, Eindhoven, Assen and Heerlen, respectively. Cumulative amounts of P in crops and drainage water for the 1972/78 period are presented in Figure 3. It is clear from this Figure that there are large differences among the sludges. With the crops grown on the sludge from Leeuwarden nearly 3 000 kg P9O5 was removed per ha, or on average, about 400 kg/year. That is an enormous amount, due to the large P supply, but also to the fact that uptake per unit of surface area is always greater for pots than under field conditions, because crops in pots profit by the open space around the pots.
-245-

P205 i n crops (kg/ha) 4 000r

6000 P205 indrainagewater (kg/ha)

Fig. 3.

C umulative amounts of phosphorus in crops and drainage water from six air-dried sewage sludges in the period 1972/78.

The amounts of P in the crops are lower for the sludges from Apeldoorn, Leiden, Eindhoven and Assen than for the sludge from Leeuwarden. For the sludges from Apeldoorn, Eindhoven and Assen this is in accordance with the P content of the sludges, but not for the sludge from Leiden, where P uptake by crops was extremely low. This was due to heavy metal effects. As far as there was any growth, crops showed severe symptoms of excess heavy metals, especially nickel. P removal by crops was largest for the sludge from Heerlen and from this sludge also an enormous amount of P (2 500 kg P20[-/ha in seven years) disappeared with the drainage water. The only explanation for this phenomenon is the acid reaction of the drainage water from this sludge. The validity
246-

of this explanation is strengthened by the fact that a still larger amount of P in the drainage water from the sludge from Leiden is accompanied by a still lower pH of this drainage water. Of course, the large amount of P in the drainage water from the sludge from Leiden may be due in part to the low amount taken up by the crop, but from the amounts of P in the drainage water from the other sludges it can be concluded that this factor had little effect, because for these sludges the amounts of P in the drainage water are quite comparable with those in the drainage water from the sludges left fallow in the previous experiment. Table 1 gives the amounts of P in the crops and the drainage water in the period 1972/78 as percentages of the amount of P in the sludges? allowance having been made for an uptake by the crops of 20% of the P supplied in mineral form. The exceptional behaviour of the sludges from Leiden and Heerlen is evident again from this Table. There is not much difference among the other sludges. In a relative sense, very little of the sludge-P has been removed in this length of time and for the normal sludges this is especially true for P removed with drainage water.
TABLE 1 PHOSPHORUS REMOVED BY CROPS AND DRAINAGE WATER FROM AIR-DRIED SEWAGE SLUDGES, USED AS PLANT SUBSTRATES, IN THE PERIOD 1972/78, IN % OF PHOSPHORUS IN THE

SLUDGES Sludge Crops Drainage water Sum Leeuwarden Apeldoorn Leiden Eindhoven Assen Heerlen 1.69 0.13 1.82
1.65 0.08 1.73 0.01 3.09 3.10 1.33 0.33 1.66 1.71 0.12 1.83 2.38 1.82 4.20

247-

3. MIXTURES OF SOILS AND AIR-DRIED SEWAGE SLUDGE The sludge from Leeuwarden, a sludge from mainly domestic waste waters, was mixed with a light sandy soil and a heavy clay soil in the following soil/sludge ratios: 100/0, 95/5, 90/10, 80/20, 60/40, 30/70 and 0/100. This experiment was conducted in the same way as was described under 2, except that more P (and N) as fertiliser was supplied as the proportion of soil in the mixture increased. The amounts of fertiliser P as P 25 o v e r t n e 19 72/78 period were, in the order of the soil/ sludge ratios mentioned above, 930, 925, 920, 910, 890, 860 and 830 kg/ha. The sandy soil contained, on a hectare basis, 8 800 kg P 2 5' t h e c l a v soil 12 100 kg. Cumulative amounts of P, taken up by the crops and leached with the drainage water in the 1972/78 period are presented in Figure 4. With increasing proportions of sludge in the mixture, there is a strong increase in the amount of P in the crops, due to an increase in the yields as well as in the P concentrations of the crops. There is a similar effect on the amount of P in the drainage water, but much less pronounced. In comparison with the crops, the amount of P in the drainage water is very low, in contrast with nitrogen (De Haan, 19 80). In Table 2, P in crops and drainage water, originating from the sludge in the 1972/78 period, is expressed in % of the P in the sludge at the beginning of the experiment, both for the sandy and the clay soil/sludge mixtures. To calculate these figures, for fertiliser P an uptake of 20% by the crops and no leaching has been assumed. Then for soil P, rates of 2.7 and 7.0% for plant uptake and 0.15 and 0.13% for leaching could be calculated for the sandy and clay soil, respectively, and then for sludge P the values of Table 2. It is evident from this Table that the values for uptake by the crop increase with decreasing proportions of the sludge in the mixture, but even with 5% sludge in the mixture the value is rather low, namely about 9% in seven years. There are no great differences

248-

P205 in crops (kg/ha) 3000

2000

1000 -

1972

1973

1000 LU-JL_ . 40 70 100 P205 in 0 510 20 air-dried sewage sludge, drainogewater (kg/ha) % by volume Fig. 4. Cumulative amounts of phosphorus in crops and drainage water from sandy soil/sewage sludge-mixtures in the period 1972/78.

TABLE 2 PERCENTAGE OF PHOSPHORUS, TAKEN UP BY CROPS AND LEACHED IN A SEVEN YEAR PERIOD FROM SEWAGE SLUDGE IN SOIL/SLUDGE-MIXTURES, AS DEPENDENT ON THE PERCENTAGE OF AIR-DRIED SEWAGE SLUDGE IN THE MIXTURE % by vol. sewage sludge O 5 lO 20 40 70

loo

Sandy soil/sewage sludge-mixtures Crops Drainage water 2.70* 0.15* 8.34 0.06 6.85 0.00 4.46 0.05 3.05 0.09 2.12 0.09 1.69 0.13

Clay soil/sewage sludge-mixtures Crops Drainage water 7.17* 0.13* 9.89 0.07 7.29 0.20 4.09 0.13 2.99 0.13 2.06 0.12 1.69 0.13

Values for soil P

249-

among the soils, but at the lower sludge rates, values are lower for the sandy soil/sludge mixtures, both for uptake by the crop and leaching, and there might be some fixation of sludge P by the sandy soil. 4. LIQUID SEWAGE SLUDGES AS ORGANIC FERTILISERS FOR GRASSLAND AND ARABLE LAND Two sludges, from the towns of Almelo and Alkmaar, respectively, were applied in amounts of 0, 1\, 15 and 22^ tons. DM/ha/year since 19 72 to a sandy soil in vessels as described earlier. The sludge from Almelo has a rather high heavy metal content, especially Cd, Cu and Ni; the sludge from Alkmaar is from mainly domestic waste water. It is the intention to apply the sludges in ten successive years, in order to create a situation which in practice, when sludge is applied, will arise only in a minimum of 100 years, because of an agreement stipulating that sludge will not be applied in amounts larger than 2 tons DM/ha/year. Half the number of vessels are treated as grassland and the other half as arable land, with the same crops as in the previous experiments, except 19 73, when maize was grown instead of grass. N and P application in mineral form was reduced in accordance with the amounts of sludge applied. In the 1972/78 period the amounts of fertiliser P applied as P , 0 , - in kg/ha were 1 080, 780, 480 and 180 for grassland and 1 020, 713, 407 and 100 for arable land at sludge application rates of 0, 1\, 15 and 22^ tons DM/ha/year, respectively. The amounts of P in kg/ha P 2 0 5 , applied as sludge, were 0, 3 176, 6 535 and 9 529 for the sludge from Almelo and 0, 2 378, 4 757 and 7 135 for the sludge from Alkmaar. The soil contained 8 800 kg P2c P e r n a Figure 5 presents cumulative amounts of P in grass and drainage water from the grassland over the 1972/78 period. It is evident from this figure that P uptake by grass was promoted more by the sludge from Almelo than by the sludge from Alkmaar.

250-

There w a s n o e f f e c t of sludge application on t h e amount of P in the drainage w a t e r , w h i c h w a s very low (less than 2 0 k g / h a in seven y e a r s ) . It should b e noticed that in this experiment sludge w a s n o t m i x e d through t h e w h o l e p r o f i l e , b u t in t h e case of grassland it w a s applied on top of the s o d , w h i c h w a s broken u p every t w o or three years and m i x e d through the upper 20 cm of the 60 cm deep p r o f i l e . the s a m e . through t h e 20 cm t o p layer. Sub-soil and top-soil w e r e In the case of arable land, sludge w a s always m i x e d

P205 i n grass (kg/ha)

P,0cin drainagewater, (kg/ha) 0

i_ _i

7.5 Almelo

15

22.5 0 75 .15 22.5 liquid sewage sludge in tons DM/ha/year Alkmaar

Fig. 5. Amount of phosphorus in grass and drainage water from permanent grassland, cumulative over the period 1972/78. The e f f e c t of sludge application on t h e amount of P in the crops and drainage w a t e r from t h e arable soil is presented in F i g u r e 6. H e r e t h e first experimental year is left out of c o n s i d e r a t i o n , b e c a u s e n o crop analyses w e r e m a d e in this year. It appears from F i g u r e 6 that in 1973 and 1974 P uptake b y crops w a s increased m o r e b y the A l m e l o than b y t h e A l k m a a r s l u d g e , b u t in t h e following years it w a s just t h e r e v e r s e ,
251-

because of negative effects on yields, due almost certainly to the heavy metals, especially nickel, in the Almelo sludge. Also for arable land there was no effect of sewage sludge on the amount of P in the drainage water.

P 2 0 5 in crops (kg/ha) 1200r 1000 800

6qo
4 00 200

P205 in drainagewater Ikg/ha) 7.5 15 22.5 0 75 15 22.5 liquid sewage sludge in tons, DM /ha/year Alkmaar

Almelo

F i g . 6.

Amount of phosphorus i n crops and drainage water from a r a b l e land, cumulative over t h e p e r i o d 1973/78.

Table 3 p r e s e n t s percentages of P taken up by the crops from the sewage sludges in the 1972/78 period for grassland and the 1973/78 period for arable land, assuming an uptake of 20% for f e r t i l i s e r P and no e f f e c t of sludge on uptake of s o i l P. On g r a s s l a n d , 15 t o 10% of sludge P was taken up by the crop depending on the sludge a p p l i c a t i o n r a t e . For arable land the percentages were higher for the sludge from Alkmaar, but lower for the sludge from Almelo. I n comparison with the previous experiments, values for uptake of sludge P are r a t h e r high, varying from 50 - 100% of the (assumed) value for f e r t i l i s e r P.

252-

TABLE 3 MEAN VALUES FOR PERCENTAGES OF PHOSPHORUS FROM SEWAGE S L U D G E S , TAKEN UP B Y CROPS IN T H E PERIOD 1972/78 FOR GRASSLAND AND 1973/78 FOR ARABLE LAND

Sewage sludge Amount, t D M/ha/year

Almelo

Alkmaar 22>j

7 5

15

7 * 5

15

22>j

Grassland Arable land

15.1

12.6

10.5

14.9 21.1

12.0 14.6

9.8
14.2

9.1

9.6

9.8

REFERENCE

Haan, S. d e , 1980.

Effect of nitrogen in sewage sludge on nitrogen in Report on the 2nd Session of Working

crops and drainage water.

Party 4 of the EEC Concerted Action Treatment and Use of Sewage Sludges in D ijon 26/28 September 1979.

DISCUSSION R.E. White (UK) In your Figure 2 you suggested that the lower leaching of phosphorus from the one sewage sludge was due to its high heavy metal content: are you suggesting that heavy metals immobilise phosphate in the sludge, and what kind of heavy metals are they? Secondly, in Figure 3 where you had high leaching from two of your sludges, you said that this was due to the acid drainage water. Can you tell us how acid the drainage water was, what was the pH?
S. de Haan (Netherlands)

On the last question, in that case the pH was 6; the others were all 7 or above.

253

On the first question, the same applied for nitrogen and for phosphorus in that particular case the amount of nitrogen leached was much lower than with the other sludges. So it could be due to prevention of decomposition of the organic matter by these heavy metals but on the other hand, most of the phosphate in the sewage sludge is not in organic form so from that point of view it seems unlikely. A. Dam Kofoed (Denmark) I was interested to learn from Dr. de Haan that you use 2 the word 'drainage water' for a surface area of 0.2 m and a depth of 0.7 m. Would it not be more correct to talk about 'leaching water' because drainage water really means water that comes through a drain, as I understand it. I think it might be con fusing. S. de Haan The experiment was set up so that we got as much drainage water as the normal precipitation surplus, about 300 mm. I had a small outlet, but I think it is more percolation water or leachate it may be a question of language. A. Cottenie (Belgium) I think it is also a question of technique. You might have analysed the drainage water or the percolation water it is not the same. S. de Haan I took it from the ditch. A. Cottenie Leaching water.

254-

PHOSPHORUS BALANC E AFTER THE APPLICATION OF SEWAGE SLUDGE H. Kick Agrikulturchemisches Institut der UniversitSt Bonn, 53 Bonn, Meckenheimer Allee 176, Federal Republic of Germany.
ABSTRACT

1. cleaning

The phosphates plants system.

of sewage sludges phosphate

from municipal fraction

sewage

water to be the evaluated

are found in different The organic

forms of bond according can mostly content. to about under our equivalent

treatment

on the basis 2.

of 20% or more of the total P supply of sludge P for

An annual

corresponding cropping

100 kg P JDJha climatic to the usual

may largely conditions phosphate S. yield

be sufficient fertilisers. 20 year about

intensive

and can be considered

as practically

In this

long term field units independent

experiment

with

50% root yearly

crops annual

and of

50% cereals, 150 kg P 20s

60 kg/ha P?0

% s been removed by an average of an average

of 118 dt cereal

supply

or 100 kg P 20y supply (after only the sludge effect) phosphates small some were added;

In the year of sludge in the years of phosphate in the total that quantity without fertiliser supply. sludge

in some cases to compensate equivalent 1974).

quantities deficiencies demonstrate

were used in order The experiment

described,

and others,

the total P

of sewage sludge

is practically P ( latzen,

to the same

in a mineral P -fertiliser

255

INTRODUCTION In sewage sludges the total N content is mostly not very different from the total P25 c o n t e n t , but according to our pot and long term field experiments about 30% of the total nitrogen corresponds well with the efficiency of the same amount of nitrogen in mineral nitrogen fertiliser. Twenty percent is adequate, if the sludges are largely dehydrated. On the basis of 30% total N content, the sludge often contains considerably more than a sufficient supply of phosphorus, because the P-pCv content is in every case high enough and a phosphorus excess can be consumed by the following crop without sludge supply. The nitrogen after-effect of sewage sludge is small, notwithstanding the high quantity of total N used in order to satisfy the nitrogen demand of the first crop. An annual sludge supply on the N basis increases the P content of the soil substantially. The sludge phosphate availability may depend on the form of phosphates, which can be very different. A fractionation by the Chang and Jackson method elaborated for soils (Chang and Jackson, 1957), but not accepted without modification in every case by other research workers (Kurmies, 1972), gives more indications of this problem (Table 1). Fe and Al bound phosphates prevail, depending on the sewage water treatment; the organic phosphate, which is considered as poorly available, reaches 20 to 30% of the total P. Ca and Al bound phosphate are considered as the most important P source for the crops (Daiber, 1958). In sludges this may prove to be true, because the sludge phosphates are not considered to be in a consolidated or crystallised state (Ivanov and Sauerbeck, 1972; Cervenka and Timmermann, 1975; Kumar, 1976), but rather to occur in a more amorphous state. It is difficult to estimate the availability of the organic phosphates. Nucleoproteides are more quickly desegregated as phytates (Ivanov and Sauerbeck, 1972).

-256-

TABLE 1 FRACTIONATION OF THE PHOSPHATES IN SEWAGE SLUDGES (Fenke, 1968). Trial Source
%P

Phosphorus fractions 25 % Al-P 5.7 5.8 14.1 15.1 8.3 10.6 34.8 34.0 24.6 % Fe-P %Ca-P 21.1 21.5 22.8 22.2 12.9 14.9 33.5 27.1 23.5 % Al-P 0.8 0.9 0.4 0.5 0.5 0.7 1.0 0.7 1.0 % Fe-P 0.5 0.6 0.2 0.2 0.4 0.2 0.9 1.4 1.2

%
26.7 28.8 18.3 22.2 24.0 24.9 18.3 20.0 12.7

1 2 3 4 5 6 7 8 9

Duisburg
i i

3.17 3.35 8.87 8.83 6.33 7.32 2.18 2.14 2.23

42.3 39.5 43.7 37.8 52.9 43.4 9.1 12.0 34.5

i i

I I

Viersen
II

Bonn
II

I I

POT EXPERIMENTS In a two year pot experiment with sewage sludge and 4 consecutive crops (barley, mustard, oats and feed rye) with a N : P25 : K 2 ratio of about 1 : 1 : 2 and with an estimated N utilisation of 30% and P utilisation of about 30 - 50% (Table 2) in the first year,the mineral fertilisation produced higher yields; in the second year the sludge was more effective. The total yield output of the sludge reached 85 to 96% of the mineral fertiliser (Table 3). The utilisation of the total sludge nitrogen and phosphorus reached 15 to 27% and 8 to 15% respectively (Table 3) . In another pot experiment on a sandy soil and loess loam soil with Lolium multiflorum (4 cuts, estimated N utilisation 25% of the total N) an additional mineral phosphate fertilisation was inefficient, but the P uptake by the crop was higher than the P uptake from the sludge phosphorus (Table 4). The insufficient potash supply by the sludge is clearly demonstrated here. In the sandy soil the real utilisation of the sludge nitrogen reaches 21 to 24%, and in the loess loam, 27 to 29%. This corresponds very nearly to the estimated efficiency. The utilisation of the total sludge pH phosphorus reached only 7 to 10% in the sandy soil (Table 5), though this soil responded very strongly to P fertilisation. In the loess loam with a higher natural P content the utilisation also reached 10%. FIELD EXPERIMENTS (Tables 6, 7) The phosphate utilisation coefficient and the P balance for practical conditions should be derived from field experiments. As an example, a 20 year running field experiment 'Parabraunerde' on loess with sewage sludge, partially combined with straw manure and green manure (vetch with rye and feed rye) will be discussed. At the beginning the soil had a pH (n/10 KC1) of 6.0, 11 mg P205/100 g, 10.9 mg K20/100 g, 0.97 organic carbon, and silt + clay < 0.02 mm 37.2% (double lactate method).

258-

TABLE 2 POT EXPERIMENT WITH DIFFERENT CROPS AND SEWAGE SLUDGE (Buck, 1952) g/pot mineral ferilisation N 0.5 1.0 2.0
P

1 year - yield Spring barley Grain 9.0 0.3 15.0 2.1 14.1 1.9 Straw 22.7 0.8 31.6 0.7 39.8 1.7 Mustard green 12.2 0.3 19.8 0.5 25.8 0.9

2 year - yield Oats Grain 2.9 0.1 4.2 + 0.1 5.2 0.7 Straw 7.9 0.1 9.0 0.5 11.6 0.9 Fodder rye (green) 1.55 0.14 1.92 0.01 1.69 + 0.26

25

K20 1.0 2.0 4.0

0.60 0.90 1.40

Nutrients in supplied sewage sludge 1.5 3.0 6.0 1.38 2.77 5.53

Mineral 1.0 2.0 4.0 10.0 1.9 10.9 1.4 18.1 + 3.7 0.75 + 0.2 21.0 1.0 27.3 1.7 28.6 1.7 9.5 0.1 5.2 0.6 7.3 0.2 7.9 2.1 1.3 9.1 5.4 0.3 6.5 0.3 12.1 0.5 2.4 0.3 10.7 0.7 15.5 0.8 20.5 0.2 5.9 0.2 1.79 0.11 1.92 0.17 2.98 0.37 1.28 0.06

TABLE 3 POT EXPERIMENT WITH DIFFERENT CROPS AND SEWAGE SLUDGE (Ivanov and Sauerbeck, 1972) Mineral fertilisation, g/pot N 0.5 1.0 2.0 P2Os 0.60 0.90 1.40 K20 1.0 2.0 4.0 Total DM yield g/pot Utilisation % P 34 36 33 N 85 90 82

56.2 81.5 98.2

Nutrients in supplied sewage sludge 1.5 3.0 6.0 1.38 2.77 5.53

Mineral 1.0 2.0 4.0 54.0 69.4 90.0 21.1 15 11 8 27 22 15

TABLE 4 POT EXPERIMENT WITH Lolium multiflorum (4 cuts) Sandy soil DM yield, g/pot (Platzen, 1970) Loess loam DM yield, g/pot P O -removal in mg/pot Sand 490 70 470 Loess 780 460 730

Mineral fertilisation, g/pot N p o, K 0

2.2 2.2 2.2

1.0 1.0

1.0 1-0 -

59.8 2.2 22.9 0.6 57.4 1.5

80.1 0.6 73.8 0.7 75.0 0.2

Fertilisation with sewage sludge (SSL) SSL kg/pot 3kg+) 3 kg 3 kg 3 kg 3 kg 3 kg Mineral fertilisation g/pot

0.5 1.0

82.0 0.7 78.3 0.5 77.6 3.8 0.5 1.0 1.0 84.9 1.0 88.0 1.7 89.0 + 0.8

105.1 0.6 103.7 2.1 102.9 0.9 109.7 1.9 115.1 + 2.0 109.4 2.8

900 1 370 1 280 1 100 960 1 440

1 370 1 330 1 510 1 400 1 260 1 420

1.0

+ ) 3 kg sewage sludge (SSL) contain 8.5 g N, 13.0 g P 52

TABLE 5 PERCENT UTILISATION OF P AND N FERTILISER IN A POT EXPERIMENT (Platzen, 1970) % utili sation sandy soil N P 53 25 48 42

Supply g/pot N Mineral fertiliser 2.2 2.2 2.2

P

25

K20 1.0 1.0

% utilisation loess loam N P 71 76 73 32

1.0

1.0

40

27

Sewage sludge

8.5 8.5 8.5 8.5 8.5 8.5

13.0 13.5 14.0 13.0 13.0 13.0

_ 0.5 1.0 1.0

24 23 21 22 23 24

7 10 9 8 7 10

27 27 27 28 29 27

10 10 11 11 10 10

TABLE 6 ROTATION
1

1960 1961 1962

+)

Sugar beet Potatoes + mustard Oats Potatoes Fodder beet Winter wheat Oats

1963 +) 1964 1965 1966 1967 1968 1969 1970 1971 1972 +) 1973 1974 + ) 1975 1976 +) 1977 1978 1979
+) +) +)

Potatoes Fodder beet Spring barley Sugar beet Winter wheat Sugar beet Oats Sugar beet Winter wheat Potatoes Spring barley Sugar beet Corn

+)Sewage sludge applied

In the rotation the sewage sludge was applied only to sugar beets and potatoes (Table 6 ) . Super-phosphate and Thomas scories provided the mineral P supply in the treatments without sludge. The after effect of the sludge phosphorus with the cereals and fodder beets can be seen in (Tables 7, 8 and 9). The soil of this field experiment is not particularly poor in phosphorus as classified by the soil testing systems, and we observed that in a phosphorus fertiliser experiment on the same field a significant decrease of yields of 8 to 10% is reached after 8 to 10 years of cropping. In the treatment 'without P' the double lactate method shows after 8
263-

TABLE 7 FERTILISATION AND AVERAGE YIELD AS CEREAL UNITS FROM A FIELD EXPERIMENT (1960 - 1979) WITH SEWAGE SLUDGE AND STRAW Treatment Average supply, kg/ha N NPK 65 dt straw 91.0 t SSL 65 dt straw 45.5 t SSL +> 65 dt straw vetches rye 93.0 t SSL + ) 65 dt straw feed rye 50 t farmyard manure 65 dt straw NPK 129 190 149 130 199 130 188 126
P

% of mineral fertiliser N 100 46 68 lOO 44 1O0 48 98

P

Mean yield, dt/ha cereal units 116.1 119.8 116.8 118.1 120.3 116.3 121.1 116.8

25 96 157 lOO 95 155 95 112 95

K20 262 160 158 155 165 150 212 155

25

K20 100 93 96 96 97 96 46 96

loo
18 37

loo
17 99 30 99

+) 8 times in 20 years.

TABLE 8 FERTILISATION, POTATO AND SUGAR BEET YIELD FROM A FIELD EXPERIMENT (I960 - 1979) WITH SEWAGE SLUDGE AND STRAW
Total supply, kg/ha N NPK 65 dt straw 91.0 t SSL 65 dt straw 45.5 t SSL
+) P

% of mineral fertiliser N
P

Potatoes, t/ha

Sugar beet t/ha

25 96 157 lOO 95 155 95 112 95

25

4 years 29.7 28.7 28.0 30.4 29.0 29.6 29.0 30.9

5 years 47.7 49.1 48.6 48.9 48.7 47.1 50.2 48.1

124 190 149 130 199 130 188 126

161 160 158 155 165 150 212 155

100 46 68 100 44 100 48 98

loo
18 37 100 17 99 30 99

65 dt straw vetches-rye 93.0 t SSL +> 65 dt straw + rye 50 t farmyard manure 65 dt straw NPK

+) 8 times in 20 years

TABLE 9 FERTILISATION AND CEREAL YIELD OF A FIELD EXPERIMENT (1960 - 1979) WITH SEWAGE SLUDGE AND STRAW Average supply, kg/ha N NPK 65 dt straw 91.0 t SSL 65 dt straw 45.5 t SSL 65 dt straw vetches + rye 93.0 t SSL 65 dt straw feed rye 50 t farmyard manure 65 t straw NPK 129 190 149 130 199 130 188 126
P

Treatment

% of nineral ferti U s e r N 100 46 68 100 44 100 48 98

P

Cereals dt grain/ha 0 9 years 52.9 53.7 52.9 52.9 53.5 53.7 54.5 53.4

Fodder beet dt/ha

25 96 157 lOO 95 155 95 112 95

K20 161 160 160 155 155 165 212 155

25 lOO 17 37 100 17 99 30 99

2 years 770 777 799 789 760 764 884 767 ++)

8 times in 20 years

Significant.

years only 5 mg P90_/100 g soil which corresponds at the same point to a decrease of the average yearly phosphate removal from 61 kg P-Oc/ha to 51 kg P20r in face of an average yearly supply of 113 kg P205/ha (Poletschny et al., 1968). In all the treatments of the sludge trial a statistically significant difference between the after effect of the mineral P supply by fertilisers and sewage sludge phosphorus did not appear. Also the average yearly supply of about 20 t of farmyard manure and 36.6 t sewage sludge (10 - 12% DM) did not have a statistically significant effect upon the yields, compared with the mineral fertilisation", the same applies to the treatments with straw manure and green manure. Only the higher nutrient supply (30% of the total N estimated as available) was efficient. The sludge providing 60% of the total phosphate supply was equivalent to comparable mineral fertilisation. This applies particularly to the root crops which received the sludge with, or without, straw. Straw did not affect the yield (Table 7 ) . The cereals which with all treatments gave the same average grain yield, included the grain maize 1979 which received 160 kg nitrogen, 200 kg P25 an<3 300 kg K_0/ha and yielded, on average, 72 dt grain/ha. Some differences between the treatments were not significant; the fodder beets reached positively to the farmyard manure treatment only once. This superiority occurred in one year yield, apparently produced by the higher nitrogen supply from sludge (Table 9 ) . Phosphate being translocated to deeper soil layers in limited quantities, losses are insignificant and a balance can be struck by the supply and the removal. The enrichment in the soil can be calculated. According to the yields the combination of sludge nutrients with mineral fertiliser nutrients did not have an effect, only a certain dependence upon the level of nitrogen supply was observed.

267-

TABLE 10 P-BALANCE, FIELD EXPERIMENT (1960 - 1979) kg/ha P 2 0 5 supply 1 2 3 4 5 6 7 8 NPK 65 dt straw 91.O t SSL 65 dt straw 45.5 t SSL 65 dt straw vetches + rye 93.0 t SSL 1 920 3 049 2 003 1 903 3 113 1 903 2 242 1 903 kg/ha total removal 1 156 1 204 1 116 1 170 1 220 1 167 1 209 1 163 yearly 58 60 58 58 61 58 60 58

Treatment

65 dt straw + feed rye 50 t farmyard manure 65 dt straw + NPK

TABLE 11 pH mg P 0/100 g SOIL ACCORDING TO DOUBLE LACTATE METHOD kg/ha P 0 5 supply 1 920 +) 3 079 2 003 +) 1 903 3 113 1 903 2 242 1 903
+)

Treatment

PH

1959

++) pH 1979 6.2 6.3 6.3 6.4 6.2 6.3 6.2 6.4

1959

mg P2O5 1970 12.4 13.9 11.6 12.0 13.4 12.7 11.2 12.7

1979 15.4 14.8 13.7 14.6

+++)

NPK 65 dt straw 91.0 t SSL

6.0 6.0 6.0 6.1 6.1 5.9 6.0 6.0

8.5 8.2 7.5 7.9 9.0 7.5 8.8 7.7

+) 65 dt straw 45.5 t SSL

65 dt straw vetches + rye

93.0 t SSL + )

15.4 14.2 17.1 14.3

+) 65 dt straw + rye 50 t farmyard manure 65 dt straw NPK +++)

'N/10 kcl

0.01 m CaCl

CAL-method

P BALANCE (Table 10) The P removal is practically equal with all treatments as shown by the uniformity of the yields. The percentage utilisation of the fertilisation phosphates with regard to soil phosphorus, can be evalulated as 10% in the first 8 - 1 0 years by comparison with the quoted phosphate trial (Poletschny et al., 1968). As soon as the soil phosphorus content decreases the utilisation of the supplied phosphorus will increase. As the removal of P with the high phosphate supply and with the low supply is 60- kg; the P reserves in the soil are enriched (Table 11), as the values of the soil testing demonstrate (double lactate method, according to Egner-Riehm). This increase does not correspond with the absolute increase, because the soil testing method used does not take account of all the phosphorus fractions; only a 200 - 250 kg/ha increase is indicated, which means only 10 - 27% of the total P quantity remaining in the soil. The pH of the soil is about 6.3 and was essentially unchanged during a period of 20 years. The reason for this discrepancy was not investigated. It may be that the remaining bulk of sludge and fertiliser phosphates reacts gradually with the soil until an equilibrium is formed in the same way as a solution equilibrium, where the lactate soluble, or readily soluble, becomes constant independently of the quantity of the solid phase.

270-

REFERENCES Buck, K. , 1952. Untersuchungen tiber die Beurteilung, Aufbereitung und Diss.

Anwendung von stadtischem Kiarschlamm als Dtingemittel. Stuttgart-Hohenheim. Cervenka, L. and Timmermann, F., 1975. der Landwirtschaft. Soil. Sci. 101, 459. Daiber, L., 1958.

Phosphatfallungsprodukte aus

biologisch geklarten Abwassern und ihre VerwendungsmBglichkeiten in Vortrag VDLUFA-Kongress Mannheim. Fractionation of soil phosphorus. Chang, S.C. and Jackson, L.M., 1957.

Beziehungen zwischen den laktatlflslichen und den Phosphaten in 3 schweren kalkhaltigen Bfiden Diss. Bonn.

pflanzenverfugbaren Nordrhein-Westfalens. Fenke, K.H., 1968.

Der Anteil an organisch gebundener P-0,- sowie der an Diplomarbeit Univers. Bonn, Landw. Fakultat. Phosphatumwandlung und Pflanzen-

Ca und Sesqui-oxide gebundenen P9O5 in Abwasserklarschlammen und Mflllkomposten. Ivanov, P. and Sauerbeck, D., 1972. Bflden.

verftlgbarkeit anorganischer Phosphatfraktionen in verschiedenen Landwirtsch. Forsch. 27/1 Sonderheft, 171. tiber die Phosphat-Elimination in den Systemen Kumar, Gupta Satish, 1976. phosphat. 29_, 118. Platzen, H., 1970. Gefass- und Lysimeterversuche zur Verwertung hoher Diss. Bonn. Mflllklarschlammkompost) Gaben an Faulschlamm und Mflllklarschlammkompost fflr die Verbesserung nflhrstoffarmer Loss- und Sandrohbfiden. Platzen, H., 1974. Phosphatzufuhr und Ausnutzungsraten von aufbereiteten

H 3 P0. - -FeOOH und H.,P04-FeCl, und die Eigenschaften von KlarschlammInaugural Diss. Bern. Zur Fraktionierung der Bodenphosphate. Phosphorsaure Kurmies, B., 1971/72.

Siedlungsabfailen (Faulschlamm und Mflllbzw. am Beispiel von Vegetationsversuchen.

Phosphorsaure 30. Folge 2, 219. Ertragsbildung und

Poletschny, H., Kick, H. and Wflrtele, K.H., 1968. Landwirtsch. Forsch. 21, 213.

P-Entzug bei einem Dauerversuch mit vier Dflngerphosphaten.

271 -

DISCUSSION D. Sauerbeck (FRG) I am always a little bit uneasy when we make statements on the after effect. We say that we may have some 30% efficiency in the first year, 10% in the next year and almost nothing in the following years. But where does the remainder stay? It enters a big soil pool from which it cannot be differentiated and we find little difference compared with the control. But can we really say that it has no further effect? The material exists and it constitutes something like 60% of the total we have added and it cannot disappear. H. Kick (FRG) No, it does not disappear. In the case of nitrogen, our sludge experiments show that the after effect ceases after two or three years. There may be partial leaching down of the nitrogen. In the case of phosphate, you can only say that every year 100 kg of phosphate will be sufficient. You cannot have more because there will be difficulties with the crops. The only way to find the answer to the question is to do trials without phosphate supply, only nitrogen and potash, over several years. We could then see for how long the yields and uptake by the roots remains the same. In another experiment we found that after ten years of phosphate deficiency in the fertilisation we had the first decrease of yield of about 10 to 15%. But with a phosphate content of about 10 mg it will take about ten years to show a decrease in yield. On the basis of our trials we are able to make recommendations to our local farmers but, of course, conditions will vary elsewhere.

272-

ACCUMULATION OF PHOSPHORUS IN A SANDY LOAM SOIL FROM FARMYARD MANURE (FYM) AND SEWAGE SLUDGE A.E. Johnston Rothamsted Experimental Station, Harpenden, Herts, UK. ABSTRACT Between 1942 and 1961 about 1 325 t/ha of sewage sludge matter) and FYM (26% dry matter) were applied soils, proportion containing of extra about total respectively to a sandy loam soil. but increases much total leaching was little of P into Extra (55% dry soluble soils as organi treated in the P on both

11 265 and 5 140 kg P bicarbonate treated soluble

P was a much smaller than on FYM treated soils were large a percentage manures. soils sludge. of total

P on sludge

in bicarbonate affected

because

P was added.

Organic P, expressed by the different on sludge

P in soil,

There was less

the sub-soil

than where FYM was applied

even though much more P was applied

273-

INTRODUCTION The agricultural use of sewage sludge has been studied intermittently at Rothamsted since the 1850s with emphasis on the extent to which sludge could augment limited supplies of inorganic fertilisers. Crowther and Bunting (1942) and Bunting (1963) co-ordinated more than 100 field experiments testing various bulky organic manures, including sewage sludge and farmyard manure (FYM), made between 1942 and 1949 on different soils in many parts of England. Sludge treated soils never gave yields larger than those given by FYM and in some experiments yields with sludge were little better than those on unmanured soils. This was thought to be because of P fixation by heavy metals in the sludge. To justify the agricultural use of sewage sludge it is, perhaps, more important to measure its effect on soil over long periods. This paper gives results from one long-term experiment made by Rothamsted staff on the experimental farm at Woburn, in Bedfordshire, where the soils are sandy loams and loamy sands and the annual rainfall is about 625 mm. The results were given in Johnston and Wedderburn (1975) and Johnston (1975). DESCRIPTION OF THE EXPERIMENT The experiment was started in 1942, at the same time as, but not as part of, a national series of experiments made between 1942 and 1949. Unlike these experiments the one at Woburn, known as the 'Market Garden' experiment, still continues although there have been modifications. The sludge came from a sewage treatment works at Mogden, West Middlesex and was usually taken from the drying beds, although some activated and digested sludge had usually been added. The effects of the sludge were compared with those of FYM. In addition two composts were tested; one was made from sludge and straw added in the proportion of 1 to 2, the other from FYM and vegetable waste, vegetable compost, mixed in the same ratio.

These four bulky organic manures were each tested at two rates, 37.5 and 75 t/ha per year (single and double dressings respectively) of the fresh manure. These amounts are more typical of intensive vegetable production than agriculture. The average amounts of organic matter, N, P and K added in 1 tonne of fresh manure are in Table 1.
TABLE 1 AMOUNT, kg OF ORGANIC MATTER, N, P AND K, ADDED IN 1 TONNE OF FRESH MANURE, MARKET GARDEN EXPERIMENT, WOBURN 1942-67 FYM 154 6.9 4.5 7.4 Sewage sludge 231 14.2 8.3 1.0 Sludge compost 166 8.3 4.7 1.7 Vegetable compost 136 5.7 3.6 5.6

Organic matter N P K

The sludge had a large dry matter content because it was stacked in small heaps for some months before use. Dressings of sludge and sludge compost ceased after 1961 because there was concern about the amounts of zinc being added in these manures and its accumulation in the soil (Le Riche, 1968). FYM and vegetable compost were not applied after 1967; PK fertilisers were applied when the organic manures were no longer given. All plots received basal or test dressings of N fertiliser and yields were measured until 1972. Since then the plots have been in grass and no applications of fertiliser, except N, or manures have been given. EFFECTS ON SOIL ORGANIC MATTER Figure 1 shows percentage carbon in organic matter added Therefore the amount that, for all four organic manures, the top 23 cm of soil and the amount of were related by a single straight line. of organic matter (or nitrogen, not shown

-275-

3 r E o ro O o
U D
1_ CM i

v v 4o-' D D o A U X 100 7 FYM vegetable sewage sludge

J

<t-

IA

compost sludge

compost

200

300

Organic m a t t e r added, t / h a

Fig. 1. Relationship between organic matter added during 1942-51 and 1942-60 and % C in soil in 1951 and 1960. Market Garden experiment, Wobum.

in Figure 1) which accumulated in soil depended only on the quantity added and not on the form of the addition, sludge, FYM or compost. TOTAL AND SOLUBLE P IN SOIL Bicarbonate soluble P in soil, but not total P, was measurably affected by the different organic manures. Very few crops grown in this experiment were analysed so the P balance (P applied minus P removed) cannot be calculated. However in long-term experiments if the amounts of P removed in the crops are small compared to applications, or little affected by treatment, it is possible to examine the relationship between P applied and that remaining in soil. Cooke (1972) gave examples of such relationships for bicarbonate soluble P in soil and P applied in long-term experiments at Rothamsted and Saxmundham. P soluble in 0.5 M NaHCO., at pH 8.5 (Olsen, et al., 1954), bicarbonate soluble P, is now widely used in England and Wales as an analytical method. Figure 2 shows the relationship between the total P added during 1942-60 and total P in surface soil (Figure 2a) and NaHC03 soluble P (Figure 2b). For total soil P a single linear relationship accounted for 94% of the variance, though soils treated with FYM or vegetable compost are on the lower side of the fitted line because some of their P had moved into the sub-soil. Figure 2b shows that bicarbonate soluble P had increased more on soils given FYM or vegetable compost than on soils with the same amount of P in sludge or sludge straw compost. The variances accounted for by the separate linear relationships were 80% for FYM-treated soils and 93% for sludge treated soils. The much smaller solubility of P added in sewage sludge compared to that in FYM is seen more clearly when the measured increase in NaHC03 soluble P was expressed as a percentage of the increase in total soil P (Table 2 ) .

277

3000

i'

300

cn

v/
2000 en V en D 0 A

oi n 200

8
m d
o Z i 2

1000

+
a > 100 o

2a
(

2b

0 0

1 2

10

12

P added (kg/ha x 1000), 1 9 4 2 - 6 0

2 U 6 8 10 12 P added (kg/ha x 1000), 1 9 4 2 - 6 0

fertilisers,

FYM,

o vegetable c o m p o s t ,

A sewage sludge,

v sludge

compost

F i g . 2.

R e l a t i o n s h i p between P added during 1942-60 in f e r t i l i s e r s and organic manures and t o t a l and NaHC03 soluble P in s o i l in I 960. Market Garden experiment, Woburn.

TABLE 2 INCREASE IN BICARBONATE SOLUBLE P AS A PERCENTAGE OF THE MEASURED INCREASE IN TOTAL P IN SOIL IN I960. MARKET GARDEN EXPERIMENT, WOBURN Manure added dur ing 1942-60 Dressing of manure Single Double FYM Sewage sludge 3.2 3.2 Sludge compost 3.7 3.6 Vegetable compost 12.4 13.4

13.5 13.5

After 18 years of manuring,12 to 14% of the extra P from FYM remained bicarbonate soluble but only 3 to 4% of the P from sewage sludge. This is probably because much, if not all, of the water soluble P is removed at the sewage treatment works and the P remaining in the sludge has little solubility in 0.5 M NaHC03. The 12 to 14% solubility of FYM P residues is in good agreement with other results from silty clay loam soils at Rothamsted. Not all methods of estimating soluble P distinguish between the solubility of P residues from sludge and FYM. Figure 3a shows the relationship between total P in soil (0 - 23 cm) and P soluble in 0.5 M NaHC03 (Figure 3ai) and 0.3 N HC1 (Figure 3aii). The acid extracted much more P than the alkaline reagent, and the acid soluble P and total P were well related by a single linear relationship for both FYM and sludge treated oils. There was no relationship between P soluble in HaHCO., and in a modified Morgan's reagent, 0.5 N NH.Ac: 0.5 N HAc at pH 4.8 (Figure 3b). Soil organic matter derived from sewage sludge, FYM or compost had little differential effect on the solubility of inorganic fertiliser Papplied once sludge dressings ceased. For all soils the relationship between NaHC03 soluble P in 19 67 and the P applied between 1961 and 1967 (Figure 4) was linear and accounted for 86% of the variance.

279-

200 r

2000

en
.

E
o Z
If)

T 100

z
2 1000

b
3 O

3a(i)

3a(ii)

1000

2000

3000

1000

2000

3000

Total P (in 0-23cm depth of soil), m g / k g

300

<
I z in

o 6

O O o D

D D

< I

200 oa

a v o

lO

6
n
D O

++
100 ' 100

X
200

3b

P soluble

in 0.5M-NaHCOj,mg/kg

+ fertilisers, Fig. 3a. Fig. 3b.

D FYM,

o vegetable compost,

A sewage sludge, v sludge compost

Relationship between total P in soil in 1960 and bicarbonate soluble P (Figure 3ai) and soluble P in 0.3 N HCI (Figure 3aii). Relationship between bicarbonate soluble P and P soluble in a modified Morgan reagent. -280-

_g>200
IT)

E
O U I
D

z
2 100 -

m o

O (/) Q_

+ o A v
0.4

fertilisers FYM vegetable compost sewage sludge sludge compost

i 2A i

0 0 OB
1.2 1.6

j 2.0

2.8

Padded (kg/ha x 1000), 1961-67

Fig. 4. Relationship between total P added as super-phosphate during 1961-67 and bicarbonate soluble P in 1967 in soils treated with various organic manures. Market Garden experiment, Woburn.

ORGANIC P IN SOIL The amounts of organic P in 1960 in soils treated with fertilisers, sludge and FYM between 1942 and 1960 are in Table 3, which gives averages of ignition and extraction methods (Chater and Mattingly, 1980).

TABLE 3 AMOUNTS OF ORGANIC AND TOTAL P, mg/kg IN SOILS IN I960 TREATED WITH SUPER PHOSPHATE, SEWAGE SLUDGE AND FYM. MARKET GARDEN EXPERIMENT, WOBURN
Depth e r a 023 Treatment 1942 60 Organic P Total P Organic P , x 100 m \ Total P 13 12 10 12 15 10

Superphosphate Sewage sludge FYM

146 350 182 104 126 100

1 120 3 000 1 780 850 850 960

3046

Superphosphate Sewage sludge FYM

(a) Sewage sludge and FYM applied at the double dressing. There was much more organic P in soils treated with sludge, but there was no significant difference between the variously treated soils when organic P was expressed as a percentage of total P. From other work it is probably that about 25% of the extra P in FYM treated soils was added as organic P which, from the data in Table 3, would have been about 165 mg P/kg. The remaining extra organic P by analysis was only 36 mg P/kg, which is 22% of the organic P added. This value of about a quarter (Chater and Mattingly, of the added organic P remaining as organic P in soil agrees well with other results at Rothamsted 19 8 0 ) . Unfortunately the amount of organic P added in the

sewage sludges used in this experiment is not known so a similar calculation cannot be made for organic P in sewage

282

sludge. 10.9%

However, the increases in organic P were 5.5% and

of the extra total P in FYM and sludge treated soils

respectively. MOVEMENT OF P INTO THE SUBSOIL When very large amounts of P are applied to sandy soils some P will be leached down the profile and possibly contaminate underground water sources. Soils treated with inorganic P fertiliser, FYM and sewage sludge were sampled by horizons down to 60 cm in 19 60 to measure how much P had moved into the sub soil; ploughing depth was 25 to 27 cm. Table 4 gives the estimated amounts of P applied between 19 42 and 19 60 and the total and bicarbonate soluble P in each horizon sampled. TABLE 4 AMOUNTS OF P, kg/ha, APPLIED AND THE TOTAL AND BICARBONATE SOLUBLE P, mg/kg, IN THE SURFACE AND SUBSOILS OF SUPERPHOSPHATE, FYM AND SLUDGE TREATED SOILS in 1960. MARKET GARDEN EXPERIMENT, WORBURN
Manure (a) added during 1942 60 Sup erphosphate Total P applied P in soil Total Depth cm 023 3046 4660 NaHC0 3 soluble 023 3046 4660 1 120 850 790 94 73 77 3 OOO 850 770 151 69 65 1 780 176 860 176 114 109 435 Sewage sludge 11 700 FYM 5 575

(a)
Sewage sludge and F Y M applied at t h e d o u b l e d r e s s i n g .

283

Where FYM had been applied both sub-soil horizons, 30 - 46 and 46 - 60 cm, contained more P than fertiliser only Although twice as much P was applied in Other evidence (Warren plots and about 25% of the extra total P to 60 cm was in the 30 - 60 cm depth. sewage sludge as in FYM there was no extra P below 30 cm compared to fertiliser treated soils. and Johnston, 1961) suggests that most of the extra P in the sub-soils of FYM treated surface soils was inorganic P soluble in either acetic acid or sodium hydroxide; increases in organic P were small. To check that none of the large reserves of P in the surface soils of sludge treated plots had moved into the subsoils the plots sampled by horizons in 19 60 were sampled again in 19 80. The results in Table 5 show that there was some movement of P below plough depth between 1960 and 1980 on all soils. TABLE 5 BICARBONATE SOLUBLE P, mg/kg, AT VARIOUS DEPTHS IN SOIL IN 1960 AND 1980. MARKET GARDEN EXPERIMENT, WORBURN
m
4 -

-(a>

Super- phosphate Depth cm 0-23 23-40 30-46 46-60 60-76 1960 94 nd 73 77 nd 1980 112 107 91 90 79

Treatment FYM NaHCO soluble P I960 176 nd 114 109 nd 1980 152 135 122 118 113

Sewage sludge 1960 151 nd 69 65 nd 1980 144 108 83 79 63

(a)FYM and sewage sludge applied at the double dressing, FYM 1942-67, sewage
sludge 1942-61.

(b)Not determined.

-284-

H o w e v e r , there w a s still treated

less P b e l o w

30 cm on

sludge no The This

soils than on f e r t i l i s e r treated

soils s u g g e s t i n g

m o v e m e n t of P that had b e e n applied f e r t i l i s e r and s l u d g e treated P probably come applied to these soils b e t w e e n

in s e w a g e s l u d g e .

e n r i c h m e n t of t h e 30 - 46 and 46 - 60 cm h o r i z o n s on b o t h soils w a s a l m o s t 1962 and 1 9 7 2 . identical. from the large d r e s s i n g s of super-phosphate

REFERENCES Bunting, A.H., 1963. Experiments on organic manures, 1942-49. Journal of

Agricultural Science, Cambridge, 60, 121-140. Chater, M. and Mattingly, G.E.G., 1980. Rothamsted Experimental Station. Cooke, G.W., 1972. Lockwood & Son Ltd., 296 pp. Crowther, E.M. and Bunting, A.H., 1962. sludge. The manurial value of sewage A paper presented The Institute of Sewage Purification. The Changes in organic P contents of Report for 1979, Part 2, 41-61. London: Crosby soils from long continued experiments at Rothamsted and Saxmundham. Fertilising for maximum yield.

at the annual summer meeting 1942, p. 16. Johnston, A.E. and Wedderburn, R.W.M., 1975. experiment, 1942-69. treatments and yields of the crops. Report for 1974, Part 2, 79-101. Johnston, A.E., 1975. The Woburn Market Garden experiment, 1942-69. Rothamsted Experimental Station. II. Report The effects of the treatments on soil pH, soil carbon, nitrogen, phosphorus and potassium. for 1974. Le Riche, H.H., 1968. Coburn Market Garden I. A history of the experiment, details of the Rothamsted Experimental Station.

Part 2, 102-131. Metal contamination of soil in the Woburn Market

Garden experiment resulting from the application of sewage sludge. Journal of Agricultural Science, Cambridge, 71, 2O5-207. Olsen, S.R., Cole, C.V., Watanabe, F.S. and Dean, L.A., 1954. Estimation of available phosphorus in soils by extraction with sodium bicarbonate. United States Department of Agriculture. Circular

No. 939, 19 pp. Warren, R.G. and Johnston, A.E., 1961. manures: farmyard manure. for I960, 45-48. - 285 Soil organic matter and organic Report Rothamsted Experimental Station.

DISCUSSION H. Kick (FRG) In Table 1 you show quantities of N, P, K etc for 1 tonne. How many tonnes were applied? A.E. Johnston (UK) The amount of manure applied was in 37.5 or 75 tonnes/ha/ year. The experiment lasted for 20 years. So the total appli cation of phosphate from sewage sludge at the high rate was 11 700 kg and in the farmyard manure it was 5 5 70. These values are given at the top of Table 4. In the test years of 19 70/19 72, all the plots received the same dressing of nitrogen and potassium. The dressing of potassium was over 350 kg of K_0/ha and therefore was likely to swamp the residual effects of the potassium which had been applied only up to 19 6 7 in farmyard manure and only up to 1961 in the sewage sludge. I do not think we were getting any complications with potassium in that soil; the values for soil potassium were given in the very much larger writeup which is referred to in the reference list of the paper. The bicarbonate soluble P values in Table 5 are not high if you look at the difference between sewage sludge and farmyard manure but if you subtract the value on the superphosphate treated soil in Table 4 (which was 94 kg) from the values in the sewage sludge and farmyard manure treated soils, you do begin to get differences which, although not in the ratio of 1 : 2, are, in fact, more nearly correct. Unfortunately, in this experiment we did not determine the amount of phosphate which was removed in the 20 years in crops. At that time the facilities for analytical work did not allow us to analyse all the crops from every plot every year. So I am not able to do a true balance such as Dr. Furrer suggested this morning where you calculate the amount applied
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and the amount removed in the crop and subtract one from the other and relate that to what is in the soil. But you can get this general relationship between amount added and increase in total and bicarbonate soluble P if you have a large number of years and when uptake is almost identical on all soils. R. Unwin (UK) With reference to your Table 5, you suggested that in the period 1960 to 19 80 there was continuing enrichment of the subsoil by leaching of phosphorus from the applications of farmyard manure. If I understood you correctly, you attributed increases on the sludge plots to superphosphate applied in the subsequent years. Does that not apply to the farmyard manure plots? A.E. Johnston No, because the farmyard manure was applied until 196 7 whereas the slurry/sludge dressings ceased in 1961. After 196 7 phosphate was only applied in three years, 19 70, 19 71 and 19 72. D. Sauerbeck (FRG) I would like to refer to your Figure 2. Did I understand you correctly that you attribute the higher amount of bicarbonate soluble phosphorus in farmyard manure treated plots, as compared to the sewage sludge treated ones, to higher contents of soluble phosphorus in the manure? I would have assumed that it would be due to changes in soil properties, changes in pH for example, due to limestone being added with the sludge, or any kind of alkaline material. So pH may differ and therefore the P solubility in the soil may differ depending on the treatments. A.E. Johnston In this particular experiment the pH of all soils was maintained between 6.8 and 7.0 throughout the whole period of the experiment. The sludge itself was not a lime conditioned ,ludge. In point of fact, we did not change the pH by more than 0.2 of a pH unit at any time during the experiment. So I do not think it is due to differing pH effects; I think it must be something
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to do with the chemical form in which the phosphate is added in farmyard manure and in sewage sludge, and that the chemical form is rather more soluble in bicarbonate solution from farmyard treated soils. The only other possibility is that the farmyard manure, having a better carbon : nitrogen ratio than sewage sludge does, in fact, get a faster flush of biomass working, and therefore a faster conversion to mineral P. E.G. Coker (UK) Is it possible that in sewage sludge the bulk of the phosphate is in inorganic form whereas in the farmyard manure we may be thinking in terms of phosphate which may be organically bound? A.E. Johnston I do not think we have enough information to answer this question. In the paper we do give a little bit of information on what we know to be the amount of organic P in farmyard manure and it is not much more than 25%. In other words, there is a lot of inorganic phosphate in farmyard manure. Again, I think this is because most farmyard manure is stored in heaps long enough for the microbiological population to start working on it. E.G. Coker I raised this point in connection with the possibility of differences in leaching. J.S.V. McAllister (UK) I do have some information on leaching from farmyard manure which I will be showing later.
R. Gerritse (Netherlands)

In our studies we have found that inorganic phosphorus in various animal when they have an age of between 4 and you have fresh manure, fresh slurries,
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the percentage of wastes is round about 80% 6 months. However, when then the organic

phosphorus content can be as high declines to the equilibrium value wastes which are normally used on phosphates, mainly in the form of

as 60 to 80%. This rapidly of about 20%. So, 80% of the soils would be mainly inorganic calcium phosphate.

There is one other factor which might affect the sodium bicarbonate solubility of phosphorus in the soils. The animal wastes contain a lot more salts than sewage sludge and fertiliser. I have found that the chloride content of slurries can go up to about 1^ to 2 g of chloride per litre, in pig slurry, which is very high. I have also found that the salt content in the soil when you use farmyard manure or slurries will be higher than with sewage sludge and that will affect the extractability of phosphorus. It is not the migration of phosphorus but the background of salts in the soil solution that might affect the increased extractability with sodium bicarbonate. This is just surmise, I cannot be sure about it. A.E. Johnston Thank you for those comments. I think your value of about 20% of the P in farmyard manure being organic after a period of storage would agree with the sort of values we have had from many experiments at Rothamsted over very many years. I go along entirely with your point about the salts in farmyard manure, but these soil samples were taken over many years after the applications in many cases and within that period many of the readily soluble salts, like the chlorides, will have leached on this particular soil with this particular rainfall. R. Gerritse Yes, but if you use the animal wastes on a regular basis then the salt status of that soil will be higher than of the other soils. A. Cottenie You have expressed your results in mg P/kg soil. Is that the general way of expressing results or have you done it because
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i t was recommended by t h e European Commission? A.E. J o h n s t o n It is the general way. It is unfortunate that in Britain at the moment the advisory services tend to express their results on a volume basis, mg/1. In the research service, almost uni formly we express them in mg/kg. That is the standard procedure which we have used for many years.

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PHOSPHORUS IN SEWAGE SLUD GE AND ITS BEHAVIOUR IN SOIL J.H. Williams1 and E.G. Coker2 'MAFF, Woodthorne, Wolverhampton, West Midlands, UK. 2 Water Research Centre, Elder Way, Stevenage, Herts., UK.
ABSTRACT A review is presented. of the behavioural adopted c in reases aspe c ts of phosphorus in sewage related sludges to the those have

The phosphorus c ontents manure and c ompost.

of different Appli c ations

sludges,

methods of treatment found in farmyard produced phosphorus signifi c ant

in the UK, are given

and c ompared with of sewage sludge soil in this sludges

in the 0.5 M NaHCO, extrac tahle between

and studies

have shown differenc es

respect depending on the method of treatment of studies on the distribution of phosphorus large appli c ations ation that results phorus of phosphorus was less of sewage over long periods P applied was predominantly into soil

and metal c ontents. Results in the profile following showed that the c a c umul and The soils. by c rops the phos quantities

in the top 50 c m of the profile on sandy mineral of phosphorus of the

than 1% of the total

of investigations status of the test applied

the utilisation

have been somewhat variable of phosphorus

depending

on the kind of sludge, treatments.

used and the magnitude

in the sewage sludge

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INTRODUCTION The total production of sludge in England and Wales is of the order of 1.2 million tonnes of dry matter and this contains approximately 17 thousand tonnes of phosphorus. The value of sewage sludge as a source of phosphorus to agriculture must be considered in relation to the total phosphate fertiliser used in England and Wales. Assuming that 60% of sludge produced is used on agricultural land, this represents 10 thousand tonnes of phosphorus compared with 120 thousand tonnes used as inorganic fertiliser in England and Wales (1978 Statistics for Fertiliser Use); this is about 8% of the total P used. Estimates of the average availability of the phosphorus present in sewage sludges varies between 50 and 70%, although EAWAG (1977) in Switzerland suggested 80%. Thus it is likely that only 4 - 5.5% of current crop requirements for phosphorus can be met by sewage sludge as produced at present. However, in most sewage treatment works only about 35 - 50% of the phosphorus arriving at the works passes into sludge (Jenkins and Menar, 1968) . The rest passes out in effluent waters; over 90% of the phosphorus in rivers is derived from sewage effluents (Owens and Wood,19 68;Youngman, 19 75). It is now generally accepted that phosphorus concentrations in excess of 10 mg P/l may result in algal growth sufficient to interfere with water use. Where control of eutrophication in rivers and lakes is required, levels of phosphorus in effluents below 1 mg/1 are aimed for. Thus in those areas where levels of P in effluents are a problem, increasing quantities of P may in future appear in sewage sludge. Even if the overall national significance of phosphorus in sewage sludge is low, it can be highly significant to those farmers who take this material and this justifies the effort of optimising its use.

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REMOVAL OF PHOSPHORUS FROM SEWAGE AND EFFLUENTS. Prior to the use of detergents, sewage contained about 2 to 3 mg/1 inorganic phosphorus, and 0.5 to 1.0 mg/1 organic phosphorus. The use of detergents has more than trebled the levels of inorganic phosphorus in sewage. It was reported (WPRL,19 70) that a typical sample of settled sewage contained 8.9 mg total P/l of which soluble P comprised 6.9 mg/1. Most of the phosphorus in sewage sludge is in inorganic form (IWPC, 1978). In conventional sewage works a trickling filter system can be expected to remove 20 - 30% and an activated sludge plant 30 - 50% of the phosphorus (Kreissl,1971). Much of the phosphorus in aerobic sludge is taken up into the biomass, but Jenkins and Menar (19 6 7) showed that, in activated plants receiving sewage with a hardness of 400 mg/1 CaCO.., the removal of phosphorus was roughly proportional to the amount of suspended solids removal and was, in part, the result of chemical precipitation in the sludge floe; this was critically dependent on pH. According to Ryczack (19 77) the carbonphosphorus ratio in normal bacterial cells in activated sludge is about 100 - 1. The influent waters in most activated sludge plants do not contain sufficient carbon to give a high rate of phosphorus removal. During growth the phosphorus is assimilated to form nucleic acid and other organic components; in aerobic bacteria, polyphosphate granules are formed within the bacterial cells. Polyphosphates readily decompose to release orthosphosphate. During sewage treatment, about one half of the phosphorus removed in the sludge is taken out during primary sedimentation and about one half in the activated sludge process (Harkness and Jenkins,1958). In industrial sludges high in metals, appreciable amounts of phosphorus are precipitated out as metal phosphates; the above authors showed that at two works treating mainly industrial sewage, there was 6 3% soluble phosphorus compared with 84% where the sewage was of domestic origin.
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In the former, the removal of phosphate in sludge was about 70%; in the latter it was about 38%. A number of countries have investigated the reduction of phosphorus concentrations in effluent waters, particularly those where effluents discharge into inland lakes or long rivers, The Centre for Agricultural Strategy (19 78) has proposed that phosphate reduction by the replacement of phosphates in detergents by non-phosphate complexing agents such as nitriloacetic acid is preferable to investing in phosphate removal. The Water Pollution Research Laboratory (19 70) estimate that, on average, 50% of the phosphate in sewage is due to detergents, and of that, up to 70% can be replaced by NTA; the maximum reduction in sewage-borne phosphate achievable in the UK is about 35%. Thus the scope for replacement of phosphate in sewage is limited. Chemical processes for phosphorus removal are based on the introduction of calcium hydroxide, ferric chloride, or aluminium sulphate to sewage either before entry to or within the treatment plant, or to final effluent. Of these, aluminium sulphate has been most widely adopted to date (Ryczack,19 77). Precipitation with these substances can remove 66 - 9 8% of the phosphorus from sewage (Bayley,19 70). However if it were introduced throughout England and Wales this would probably cost an additional 100 - 150 million and would increase the cost of sewage treatment by 33%. It is important to realise that in the UK, since most of our large centres of population are sited on estuaries or short rivers, the problems of phosphorus pollution of inland waters are minimal and that there are only a limited number of areas where the additional cost of phosphorus removal can be justified on environmental grounds. A method of enrichment of sludge phosphorus has recently been described by several authors, based on the modification of the activated sludge process. Nicholls and Osborn (1979) describe the method, which is based on observations that obligate aerobic bacteria in the activated sludge process
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loose phosphate to the water when subject to anaerobic conditions. On return to highly aerobic conditions following such a period of stress the organisms not only make an increased phosphorus demand for the expanding biomass, but greatly increased amounts of phosphorus are laid down internally as polyphosphates. Up to 90% phosphate reduction has been claimed by several authors, with phosphorus concentrations in the activated sludge as high as 8% of dry solids (Galdieri, 19 79) , but the method is not yet regarded as sufficiently reliable for general use. PHOSPHORUS CONTENT OF DIFFERENT SLUDGES The phosphorus content of sludge varies appreciably depending on the nature of the discharges which come into the sewage treament works and the processes of sewage treatment which are adopted. Some typical analyses of different types of sludges are shown in Table 1.
TABLE 1 PHOSPHORUS CONTENT OF DIFFERENT SLUDGES (EXPRESSED AS % P,0^) (IWPC, 1978)

Sludge type

Dry matter

( % ;
Liquid Activated Liquid digested Pressed cake Digested (air-dried) 3.4 3.6 40.0 52.0

On dry solids 3.3 - 7.5 1.2 - 7.0 2.2 - 4.7 1.2 - 4.2

Mean on moist sludge 0.18 0.15 1.3 1.4

It has been estimated that approximately phosphorus present is available to the crop in application. This estimate, however, is based slim evidence and availability will not be the types of sludges. Harkness and Jenkins (1958)
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50% of the total the year of on some ratrer same for all data suggest

that up to 30% of the sludge phosphate could be present as relatively insoluble salts in sludge where the sewage is heavily contaminated with metal salts from industrial discharges, Recent unpublished data from the WRC show that the percentage of sludge-borne phosphorus extracted by 0.5 M sodium bicarbonate from fresh sludge-soil mixtures was up to 50% where fresh sedimented sludge was used, but was about half this level where liquid digested sludge was used. Where activated sludge is used the phosphorus which is present as part of the bacterial biomass is likely to be released very quickly. It is therefore important to avoid drawing general conclusions from experimental work with one particular sludge type. It seems likely that a number of the inconsistencies in published results arise from this. Calculations of the amounts of organic matter, N, P and K in a tonne of fresh manure used in the Woburn Market Garden Experiment were made by Johnston (1975) and these are shown for comparison in Table 2.
TABLE 2 ORGANIC MATTER, N, P AND K IN IT OF FRESH MANURE (kg) Sewage sludge 235 14.4 8.5 1.2

FYM Organic matter N 25 K20

P

Sludge compost 170 8.5 4.8 2.1

157 7.0 4.6 9.0

Thus, 1 tonne of sewage sludge (60% dry solids) adds more organic matter, N and P, than 1 tonne of fresh farmyard manure but contains much less K. Composting the sludge produces a material supplying much less N and P than undiluted sewage sludge. Also the composting results in an immobilisation of the total N.
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EXTRACTABILITY OF THE PHOSPHORUS IN SEWAGE SLUDGE Where the phosphorus content of the sludge has been increased by chemical precipitation, the efficiency of this phosphorus in terms of its availability to crop plants will depend on the method of precipitation adopted and the resultant solubility of the metal or calcium phosphates formed. It is conventional to assess the plant available fraction of a nutrient by extracting it with mild- chemical extractants which then need to be calibrated by relating the extractable fraction to crop response. Gupta and H3ni (19 79) investigated the relative percentage phosphate utilisation of different sewage sludges at two pH levels in pot experiments. They found a highly significant correlation between the citric acid soluble phosphate ( % of the total phosphorus content) and the relative % phosphate utilisation. The correlation between the % P-utilisation and 2% citric acid soluble P as % of total P(r) was 0.94 for an unlimed acid soil. This value for extractable P is proposed as an index for determining the plant available phosphorus content of sewage sludges. The results also showed a marked similarity between the relative % phosphate utilisation of sludge phosphate and amorphous iron phosphate. EFFECT OF SEWAGE SLUDGE APPLICATIONS ON EXTRACTABLE SOIL P The results of the classical Woburn Market Garden Experiment have been summarised by Johnston (19 75). He found that the total P in soil was well related to the P added. The interest however must be in that fraction of soil P which can be readily utilised by the plant. That fraction of soil P which is extractable with 0.5 M NaHCO, gives a good indication of plant available P and the phosphorus in FYM and vegetable compost increased the NaHCO-, soluble P much more than the sewage sludge or sludge compost. The quantities of phosphorus applied in the Market Garden Experiment over the period of 1942 - 1967, together with the resulting amounts of total and
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soluble P is shown in Table 3 below (Johnston, 1975)

TABLE 3 PHOSPHORUS APPLIED OVER THE PERIOD 1942 - 1967 AND THE RESULTING CONCENTRATIONS OF TOTAL AND NaHCO SOLUBLE P IN SOIL. Fertilisers Total P applied (kg/ha) Total P in soil (mg/kg) Depth (cm) 0 - 22.5 30 - 45 45 - 60 NaHCO soluble P (mg/kg) 0 - 22.5 30 - 45 45 - 60 94 73 77 176 114 109 151 69 65 Depth (cm) 1120 850 790 1780 960 860 3000 850 770 427 FYM 5470 Sewage sludge 11477

More than twice as much phosphorus was added in sewage sludge as in FYM but its effect on the NaHCO., soluble P was very much less particularly when the surface 60 cm of profile is considered. The subsoils of plots receiving FYM were enriched by phosphorus leached from the surface soil. Very little P moved into the subsoil of the sludge treated soil. Thus the particular sludge used cannot be regarded as an efficient phosphorus fertiliser since large quantities are required over a long period of time to raise appreciably the level of bicarbonate soluble P in the soil. Soluble phosphates will have been lost to the effluent and much of the residual P in the sludge was probably present as heavy metal phosphates. The percentage of sludge phosphorus extracted by 0.5 M Na HCO, after mixing liquid raw and digested sludges with 3 soils was determined by Coker (19 80, private communication) and the results are shown in Table 4.

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TABLE 4 PERCENT SLUDGE P RECOVERED IN 0 . 5 M NaHCO., EXTRACT AFTER MIXING WITH DIFFERENT SOILS LR LD L i q u i d raw s l u d g e " digested sludge H e a t h and Reach Loamy sane -pH 7 . 0 LR 67 133 200 Mean 52 60 51 54.3 LD 24 26 27 25.7 Everton O r g . Sand--pH 5 . 5 LR 44 42 42 42.7 LD Padstow S i l t y c l a y loam -pH 5 . 5 LR 31 28 27 28.7 LD 12 10 12 10.6

P applied (mg/kg)

21 20 20.5

The % r e c o v e r y of t h e p h o s p h o r u s from l i q u i d raw s l u d g e was more t h a n t w i c e t h a t from t h e l i q u i d d i g e s t e d s l u d g e . The r e s u l t s of s o i l a n a l y s i s f o r samples from t h e Lee V a l l e y sewage s l u d g e / m e t a l p h y t o t o x i c i t y e x p e r i m e n t p r o v i d e e v i d e n c e of i n c r e a s e s i n s o i l P f o l l o w i n g t h e a p p l i c a t i o n of 5 d i f f e r e n t s o u r c e s of s l u d g e , a l l a t 125 t / h a dry s o l i d s (Table 5)
TABLE 5 0.5 M NaHCO EXTRACTABLE P IN SURFACE SOIL 1 YEAR AND 2 YEARS AFTER THE APPLICATION OF 125 t/ha OF SLUDGE DRY SOLIDS (mg/1 P) Extractable P concentration 1969 1970 8 Very Low Low High Low High Low High Low High 154 131 101 95 55 68 19 118 130 18 194 158 133 124 94 103 29 139 174

Sludge Control

type no s l u d g e )

Metal

Domestic Zn c o n t a m i n a t e d
ii it II

Cu
II

Ni
11

II II

Cr
II

"
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Thus applications of all 5 sludges have resulted in large increases in 0.5 M NaHCO.. extractable P; these contained between 2500 and 3000 kg/ha total P25- Sludges with high concentrations of Cu and Ni and to a lesser extent Zn have resulted in a lower P extractability in soil/sludge mixtures. The phosphorus content of soil in the field after 6 years application of sewage sludge was measured by Schmid (1977). In these experiments the results from annual applications of 2 sludge types were compared with those obtained from annual applications of a mineral fertiliser in terms of total and extractable (CAL)P. The resulting soil concentrations are shown in Table 6.
TABLE 6 SOIL PHOSPHORUS CONCENTRATIONS AFTER 6 YEARS OF MINERAL FERTILISER AND SEWAGE SLUDGE APPLICATIONS !mg/kg P Sludge or fertiliser treatment Nil Mineral fertiliser (annual) 5 t/ha sludge 1 (annual) 5 t/ha sludge 2 (annual) 1972 Total 1760 1520 1810 1750 CAL 70 80 130 100 Total 1650 1680 2830 1500 25> 1973 CAL 120 100 230 160

1974 Total 1350 1500 1700 1580 CAL 120 150 220 220

P0

(%) sludge 1 - 4.0 to 5.5 sludge 2 - 3.0 to 4.0

On a v e r a g e , 30 t / h a of s l u d g e 1 o v e r a p e r i o d of 6 y e a r s h a s doubled t h e e x t r a c t a b l e s o i l P(CAL) l e v e l and somewhat l e s s f o r s l u d g e 2 compared w i t h t h e c o n t r o l and m i n e r a l f e r t i l i s e r . The 19 74 d a t a s u g g e s t t h a t 9 t o i o % of t h e p h o s p h o r u s i n t h e s e 2 s l u d g e s i s CAL e x t r a c t a b l e . E f f e c t s of c h e m i c a l t r e a t m e n t : t h e e f f e c t s of t r e a t m e n t w i t h c a l c i u m , aluminium o r i r o n on t h e b i c a r b o n a t e s o l u b l e s o i l P have b e e n s t u d i e d by Soon e t a l . (1978) and some of t h e r e s u l t s which t h e y o b t a i n e d a r e shown i n T a b l e 7.
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TABLE 7 EFFECT OF SOURCE AND RATE OF N ON 0.5 M NaHCO SOIL (O to 15 cm)

N rate Control Ca -sludge

EXTRACTABLE P IN SURFACE

Al --sludge

Fe -sludge

kg/ha N
200 400 200 400 13 13 84 84 Silt loam 50 (390) 80 (780)

mg/k g P 18 (480) 30 (960) 84 (480) 99 (960) 27 (600) 35 (1200) 81 (620) 87 (1240)

Loamy sand 128 (400) 149 (800)

Figures in parentheses denote the quantities of P (kg/ha) added over a 3 year period. The amount of P added in the various sludges is in the order Fe -sludge > Al -sludge > Ca -sludge but the NaHCO, extractable P is in the order Ca -sludge > Fe -sludge > Al sludge indicating that P in the calcium sludge is more exHowever, plant uptake data did not reflect the The Ca -sludge appeared to be a slightly tractable.

build up of soil P with the repeated sludge applications for corn and bromegrass. Fe sludge. Liquid digested sludge: the effect of liquid digested more efficient source of P for bromegrass than either Al or

sludge applications on Bray's extractable P content of the 0 to 15 and 15 to 30 cm soil horizon was measured by Kelling et al. (1977). Soil levels determined after varying periods of time are shown in Table 8. Sludge application resulted in immediate marked increase in Bray P, extractable P. However, levels decreased with time after sludge application, probably as a result of fixation; some studies have shown that, where large volumes of waste water are applied, small amounts of P may move vertically in the profile.

3 0 1

TABLE 8 AVERAGE SOIL AVAILABLE P (BRAY P, EXTRACTABLE) AS AFFECTED BY RATE OF LIQUID DIGESTED SLUDGE AND TIME AFTER APPLICATION FOR THE 0 TO 15 AND 15 TO 30 cm SOIL HORIZONS. Ti me afte r sludge application (months) Sludge treatment mt/ha dry solids 0.0 39 10 15 ppm Bray P, ext. P Silt loam 0 - 15 cm 34 116 Silt loam 15 - 30 cm 0.0 30.0 0.0 30.0 0.0 30.0 18 33 39 107 17 27 16 19 Sandy loam 0 - 15 cm 43 109 Sandy loam 15 - 30 cm 18 24 14 20 39 86 12 17 24 101 30.0 (732 kg/ha P) 151 26

DISTRIBUTION OF PHOSPHORUS IN THE PROFILE AND LEACHATE CONCENTRATIONS Four field sites in Pennysylvania, USA, which had been irrigated with different levels of secondary treated sewage for 9 to 11 years were examined for phosphorus content in the soil water extracted with suction lysimeters by Kardos and Hook (19 76) . The average orthophosphate P concentrations in the applied sewage effluent and in soil water samples are shown in Table 9 for a corn rotation area. The concentration of soluble P decreased substantially as the waste water percolated downward. At the 15 cm depth, the concentration was less than l/10th of that in the waste water. At 60 cm depth the concentration was not significantly
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greater than the control samples and at 120 cm the levels were down to background. These low concentrations have resulted in very low leakage of P (Table 10) .
TABLE 9 AVERAGE P CONCENTRATIONS IN APPLIED SEWAGE AND IN SUCTION LYSIMETERS SAMPLED AT VARIOUS DEPTHS IN THE ROTATION-CORN AREA Depth (cm) Sewage effluent Soil water Soil water Soil water 15 60 120 0 5 0 5 0 5 (control) (control) (control) Effluent amount (cm/week) P concentration (mg/1) 5.68 0.04 0.33 0.05 0.07 0.04 0.05

TABLE 10 AMOUNTS OF PHOSPHORUS ADDED IN SEWAGE OR FERTILISER OVER AN 11 YEAR PERIOD AND TOTAL AMOUNTS REMOVED IN CROP OR LEACHED BELOW 120 cm DEPTH IN SOIL Kg/ha P Corn irrigated Added P Crop P removed Leached P Corn control Added P Crop P removed Leached P 791 346 6.9 438 162 1.6

Of the total P applied in sewage, 44% was removed in the crop, less than 1% was leached out and 55% was fixed by the soil. Comparing soils, the deeper penetration of P at one site was apparently related to its lower sesquioxide content and lower clay content. At none of the sites were leaching losses greater than 3% of the ttotal P applied.

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The distribution of soil phosphorus down the profile was measured by Beek et al. (1977) following sewage application to a sandy soil. Surface flooding with raw sewage water of soil with pH 4.3 raised pH levels to between 6.5 and 6.8. Following the application to grassland at a rate of 2.5 m/year for 45 years, the accumulation of P in the soil was still pred ominantly limited to the top 50 cm even on a sandy soil. The accumulated phosphates were largely present (80 85%) as in organic phosphates mainly bound to aluminium. UTILISATION OF SLUDGE PHOSPHORUS BY CROP A field study of the agricultural use of anaerobically digested liquid sludge applied during the summer of 19 71 was conducted by Kelling et al. (1977) . The rates of the liquid digested sludge corresponded to 0.0, 3.75, 7.5, 15,30 and 60 t/ha of dry solids. Uptake and recovery of sludge P by 1 rye and 2 maize crops were measured. The very low recoveries of P obtained (lto2%) from the anaerobically digested sludge are largely due to the large amounts of P applied a minimum of 91.5 kg/ha P. Fertiliser P was not tested in these experiments but, on average, recoveries of the order of 15% would be expected for cereals and potatoes and 25% for grass leys and brassicae crops. The same workers studied the phosphorus concentration, uptake and recovery from liquid digested sludges by sorghum and 3 corn crops. The maximum cumulative recovery of sludge applied P by the 4 crops was 9% at the lowest rate of application of 18 3 kg/ha P. At the higher rates of application, recoveries were much lower. Average rates of application in the UK are much lower than this 4t/ha on arable land and 2t/ha dry solids on grassland. The effects of autumn and spring applications of liquid digested sludge on grass are being studied by Hall and Davis (19 80) . Rates of P applied range from 104 to 4 87 kg/ha P.

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Significant increases in the P content of the first cut of grass were recorded. It required 324 kg/ha sludge P applied in spring to raise the P content up to that obtained from 80 kg/ha P as superphosphate (0.32% P ) , i.e. 25% as effective as water soluble phosphate. In the case of autumn applied digested sludge similar amounts of sludge P were required to give comparable increases in the P content of the grass. Increasing amounts of spring applied P (up to 487 kg/ha) had no further effect on P content. Dried pelleted sewage sludge: a study of the effectiveness of the nitrogen and phosphorus in dried pelleted sludge was conducted by MAFF Soil Scientists at Wye (Marks, 19 78) . Perennial ryegrass was grown in a peat medium in pots. The treatments consisted of 4 rates of sludge, 4 rates of N fertiliser (as ammonium nitrate) and 4 rates of superphosphate in factorial combination. Three harvest cuts of grass were taken and analysed for N and P. The yield and offtake data indicated that the nitrogen and phosphorus in the sludge was between 9 and 12% as effective as fertiliser N and P. For nitrogen in this type of sludge, the result is perhaps not surprising but the availability of the phosphorus is much lower than would be expected. It is likely that this process drastically altered the extractability of the sludge phosphorus. PRACTICAL CONSIDERATIONS IN THE USE OF SLUDGE AS A SOURCE OF PHOSPHORUS Only part of the sewage sludge available in England and Wales is applied to agricultural land. Much of the population of the UK lives in large urban conurbations on river estuaries; for them, both on the administrative and economic grounds disposal to sea is an important option. In order to avoid metal pollution of the sea it is almost equally important for the disposal authority to reduce metal concentrations in sludge going to sea as land.

305 -

Transport costs loom large where sewage sludge is spread thinly on agricultural land; it is cheaper to dump it, but the capability to dump depends on the availability of dumping sites. Thus the major sustainable long-term outlet lies in the utilisation of sewage sludge on agricultural land, but if it is to be used efficiently consideration must be given to transporting it over greater distances from the treatment works . It is apparent that the most useful outlets both on agricultural and environmental grounds are cereals and permanent and temporary grass crops which are not particularly responsive to fertiliser phosphorus. Thus it is on these crops that It should research needs to be concentrated in order to resolve the conflicting evidence that exists at the present time. then be possible to make more informed decisions on such questions as the extent to which sludge phosphates can be utilised, what kinds of sludge are the most effective phosphate sources for different crops and the most appropriate rate and frequency of application to make the best use of sludge phosphate. REFERENCES Bayley, R.W. 1970. Nitrogen and phosphorus removal: methods and costs. Water Treatment and Examination, 19, 294-319. Beek, J., de Haan, F.A.M. and van Riemsdijk, W.H. 1977. Phosphates in soils treated with sewage water: I General Information on sewage farm, soil and treatment results. Fractionation of accumulated phosphates. J. Environ. Qual. 6^4-12. Bunting, A.H.J. 1963. Experiments on organic manures L942 - 49. Jour. Agric. Sci. 60, 121-140. Centre for Agricultural Strategy. 1978. Phosphorus; a resource for UK agriculture CAS report 2, University of Reading. Cooke, G.W. and Williams, R.J.B. 1970. Losses of nitrogen and phosphorus from agricultural land. Water treatment and examination, 19, 253-276 EAWAG (Swiss Federal Institute for Water Resources and Pollution Control) 1977. Sewage sludge as a fertiliser - economic considerations. Prof. Rep. No. 30-110. - 306-

Galdieri, J.V. 1979.

Remove phosphate biologically.

Water and Wastes

Engineering, 16, (7), 43-44. Gupta, S.K. and H^ni, H. 1979. France. (In press). Hall, J.E. and Davis, R.D. 1980. The utilisation of sewage sludge in land reclamation: results of a preliminary experiment at Wheathampstead, Herts Laboratory Report LR 1153, WRG Stevenage. 'Use of liquid digested lagooned sludge' . Harkness, J. and Jenkins, S.H. 1958. Phosphorus content of sewage during purification at various works of the Birmingham Tame and Rea District Drainage Board. J. Proc. Inst. Sew. Purif. 85-91. Institute of Water Pollution Control. 19 78. Jenkins, D. and Menar, A.B. 1967. ment Processes, part 1. Manuals of British Practice in Water Pollution Control III; Sludge Utilisation and Disposal, pp 19. The Fate of Phosphorus in Sewage TreatPrimary Sedimentation and Activated Sludge. Estimation of available phosphate content of sewage sludges. Paper presented to EEC Symposium at Cadarache,

Sanitary Engineering Research Laboratory Report No. 67-6 Berkeley, University of California. Jenkins, D. and Menar, A.B. 1968. ment processes. The fate of phosphorus in sewage treatMechanisms of enhanced phosphate removal by

activated sludge SERL Report 68-6 Berkeley Sanitary Engineering Research Laboratory, University of California. Johnston, A.E. 1975. The Woburn Market Garden Experiment, 1942 - 6 9 . II. Rothamsted Experimental Station, Report Phosphorus balance in sewage effluent The effects of the treatments on soil pH, soil carbon, nitrogen, phosphorus and potassium: for 1974, Part 2, 102-131. Kardos, L.T. and Hook, J.E. 1976. treated soils. J. Environ. Qual. 5,87-90. Kelling, K.A., Peterson, A.E., Walsh, L.M., Ryan, J.A. and Keeney, D.R. 1977. A field study of the agriculture use of sewage sludge.I. Effect on crop yield and uptake of N and P. J. Environ. Qual. 6 _ , 339-345. Kelling, K.A., Walsh, L.M., Keeney, D.R., Ryan, J.A. and Peterson, A.E. 1977. A field study of the agricultural use of sewage sludge. II. Phosphorus removal practice. Paper presented at Effect on soil N and P. J. Environ. Qual. 6 _ , 345-352. Kreissl, J.F. 1971. Marks, M.J. 1978. Conference at Sanitary Engineering Institute, March 19 71. Evaluation of the nitrogen and phosphorus content of -307-

dried pelleted sewage sludge. Soil Sdience Ann. Report, Wye Sub-centre (MAFF) . Nicholls, H.A. and Osborn, D.W. 1979. Bacterial stress; a prerequisite for biological removal of phosphorus. Jour. Water Poll. Control Fed. 51, (3), 557-569. Owens, M. and Wood,G. 1968. Some aspects of the eutrophication of water. Water Research, 2, 151-159. Ryczack, R.S. and Miller,R.D. 1977. Schmid, von R. 19 77. A review of phosphorus removal technology. US Dept., Commerce NTIS Rep. 7706. The phosphate, copper and zinc content of soil and plants after application of sewage sludge for 6 years in a field experiment. Landwirtschaftliche Forschung. 30, 125-129 Soon, Y.K., Bates, T.E. and Moyer,J.R. 1978. Land application of chemically treated sewage sludge: II Effects on plant and soil phosphorus, potassium, calcium, magnesium and soil pH. J. Environ. Qual. 7, 19 3-226. Water Pollution Research Laboratory. 1970. effluents. Youngman, R.E. 1975. Phosphates in sewage and sewage Notes on Water Pollution No. 49. Ministry of Technology. Observations on Farmoor, a eutrophic reservoir in the

Upper Thames Valley during 1965 -73. In : The effects of storage on Water Quality (Proceedings of a Water Research Centre Sypmosium), pp 163-201. The Water Research Centre, Medmeham Laboratory, Marlow, Bucks.

DISCUSSION M. Webber (Canada)

You showed that phosphorus added as animal manure moved through the soil profile whereas phosphorus added as sludge probably did not. Do you have any explanation for this different effect of the two materials? J.H. Williams (UK) No, not really. This was Rothamsted work and it was done The only thing one can

on the light loamy sand soil at Woburn.

surmise is that there must be some differences in the form of the two types of organic matter, the binding with the organic matter, and possibly the organic complexes that are formed in the two materials; one being more mobile than the other. - 308-

PHOSPHORUS ACCUMULATION IN SOIL PROFILES AND PHOSPHORUS LOSSES AFTER THE APPLICATION OF ANIMAL MANURES H. Vetter and G. Steffens Landwirtschaftliche Untersuchungs und Forschungsanstalt, Postfach 25 49, 2900 Oldenburg, Federal Republic of Germany. A3STRACT High slurry int into deeper a soil soil depth dressings layers. can cause considerable In our trials phosphorus between displacement 400 and

with P-dressings

and 1 400 kg P 0yha/year

8 to 13% of the added phosphorus

amounts moved

of 60 - 90 cm. of the phosphorus applied, displacement is influenced by:

" / ? intensity -

tie amounts of P the soil th type,

humus content

and the pH of the

soil. groundwater or drainage

An increase

of the P-contents until

in the shallow now.

water could not be determined

309-

INTRODUCTION The mobility of phosphorus in soils is relatively low. Normally only small amounts of phosphorus migrate into deeper soil layers and only very small amounts reach the groundwater table. This is the case for normal P-fertilisation, but not necessarily where high P-dressings are applied with slurry, as happens often in regions with high livestock intensities. Concerning those regions we want to discuss the following four questions: A) B) C) Will phosphorus migrate into deeper soil layers after high slurry dressings? Which factors influence the phosphorus downward displacement? Will phosphorus be leached in considerable amounts into the groundwater after long-term high slurry dressings? Which phosphorus accumulations in the soil lead to a heavy phosphorus downward displacement?

D)

A) WILL PHOSPHORUS MIGRATE INTO DEEPER SOIL LAYERS AFTER HIGH SLURRY DRESSINGS? To answer these questions we determined the phosphate contents on fields having varying long-term slurry applications, at soil depths of 0 - 30, 30 - 60 and 60 - 90 cm. All the fields were humus sands with an average organic matter content of 5.5% -and a C : N ratio of 28 : 1. Twelve of the 34 fields compared were without slurry, 22 fields had been dressed with varying amounts of slurry over the last 15 - 25 years: 8 3 fields with an average, 70 m pig slurry/ha, 8 fields with 3 3 110 m , 6 fields with 255 m . With these slurry amounts the fields received 420, 660 and 1 500 kg P205/ha/year. Figure 1 shows the phosphorus contents determined at the different soil depths (0 - 30, 30 - 60 and 60 - 90 cm) of these
- 310-

20
1

40
1

60
1

80

r~

100

120

%0
-1

12

mg P20s\100g soil (DU number of fields m3 slurry/ ha /year kg % 05/ha/year

30 cm

60 cm

90cmL soil depth

Fig. 1. P-enrichment and P-displacement in soils after different slurry applications during 20 years.

fields (mg P-0 /100 g soil, double lactate extract). The phosphorus contents in the sub-soils and deeper sub-soils are graduated in the same way as the phosphorus contents in the top soils. Soils with higher phosphorus contents in the top soil also have higher phosphorus contents in 30 - 60 and 60 90 cm soil depth. The contents of total phosphorus in the soil show still more clearly than the double lactate-P-contents, that considerable P-amounts are displaced into deeper soil layers (Figure 2 ) . Figure 3 shows the phosphorus downward displacement in kg/ha after varying high slurry dressings. After the application 3 of 70 m slurry/ha/year (420 kg P25^ approximately 800 kg P-Oj- migrated into a soil depth of 60 - 90 cm; after the application of 110 m 3/ha/year (600 kg P 2 0 g ) approximately 1 100 kg P25 and after the application of 2 55 m /ha/year approximately 2 100 kg P205'' that is respectively 13, 12 and 8% of the added amounts of P20rB) WHICH FACTORS INFLUENCE THE PHOSPHORUS DOWNWARD DISPLACEMENT? 1. The downward displacement of phosphorus applied with slurry is more intensive than the downward displacement of fertiliser-phosphorus. We determined the P-downward-displacement into deeper soil layers after application of 800 and 1 600 kg P_05/ha in the form of mineral fertiliser and slurry (Figure 4). Result: after the application of 800 kg PoOj- as mineral fertiliser, the increase of the phosphorus content (double lactate) at 60 - 90 cm soil depth was 1 mg/100 g soil; after application of the same amount in the form of slurry 7 mg/100 g soil. Applying 1 600 kg P-O^/ha in the form of mineral fertiliser the increase of the phosphorus content at 60 - 90 cm soil depth was also 1 mg/100 g soil; applying 1 600 kg P205/ha in the form of slurry, the increase was 12 mg/100 g soil. The phosphorus applied with slurry migrates faster than the phosphorus applied with mineral fertilisers, because the organic matter of the slurry favours the phosphorus migration (humate-effeet according to Flieg, 1935; Scharrer and Kuhn, 1952) and because phosphorus applied with slurry can be washed directly into the deeper soil
-312-

50
~i

100
1 1 1

150
:

200
i 1

250
1 1

300
1 1

350
1 1

WO
1

-i

50 1

500 mg R Q. 1 /100g soil (total-P) 6 number of fields slurry/ha/year $05/ha/year

12

255 m3 30 cm 1500 kg

60 cm

90 cm

soil depth

Fig. 2.

P-enrichment and P-displacement in soils after different slurry applications during 20 years.

enrichment kg P2 O^/ha (total)

26000

22000

18000 0-30 KOOO cm

10000

6000

30- 60 cm ^

2000

V13V./A 70 420 60- 90 cm >2V.A W 600 255 1350 nr slurry/ha/'year 05/ha/year

k g ^

Fig. 3. P-enrichment in the soil after different slurry applications during nearly 20 years.

-314-

increase m mg P2 05/100g soil

35 input

0-30 cm

30

800 kg

25

20

15
0-30 cm

10

30- 60 cm 60-90 cm fertilizer slurry fertilizer slurry

Fig. 4.

Increase of the P-contents in the soil (mg/lOO g soil, DL) after mineral fertilisation and slurry application. (800 and 1 600 kg P 2 O s /ha) .

315-

layers, when the soil is relatively wet and water-saturated at the time of application. 2. The amounts of P displaced into deeper soil layers (Figure 4 ) . The

increased with increasing P-dressings the P-O^-content at 60

application of 1 600 kg P 2 0 5 /ha in the form of slurry increased 90 cm about 12 mg/100 g soil; the We application of 800 kg P 2 0 /ha 'only1 about 7 mg/100 g soil, also found similar results in other field trials. 3. Applying the same phosphorus amounts on similar soils, After

the phosphorus displacement into deeper soil layers is higher on soils rich in P than on soils poor in P (Figure 5 ) . an application of approximately 2 500 kg P-OjVha during 6 years there was a downward displacement of phosphorus into 60 - 90 cm soil depth of 1 000 kg P Or/ha on the soil rich in P (40 mg P 0 5 /100 g soil, D L ) , and of 'only' 500 kg P~0 5 /ha on the soil not so rich in P (24 mg P ? 0 5 /100 g soil) .

enrichment kg P2 05/ha

(total) not so rich on P 0-30 cm

2000 r

1000 -

30-60 cm

60-90 cm
Fig. 5. P-enrichment in different soil depths on HS after 6 years dressing 40 rag/100 g soil (DL) of 90 m pig slurry/ha/year. Rich on P Not so rich on P 24 mg/lOO g soil (DL)

-316-

4. In acid soils there is a faster downward movement of phosphorus, when the soils are rich in carbon and a slower downward movement when the humus content is not so high. We compared soils, humus content 2.7%, with soils, humus content 5.8% (Figure 6 ) . On the soil with a humus content of 2.7% the downward movement into 60 - 90 cm soil depth was only 100 kg P20r/ha; on the soil with a humus content of 5.8% it was 1 000 kg P20j-/ha. Relating the amounts of P displaced to the added P-amounts, the difference between the two soils becomes still more apparent. On the soil with the lower humus content only 3% of the added amounts of P migrated into 60 - 90 cm soil depths; on the soil with the higher humus content it was 40% of the added amounts of P. This was so despite the fact that the soil with the lower humus content received higher amounts of phosphorus (4 460 kg P?0r/ha) and despite the fact that this soil already had higher P-contents in the top-soil at the beginning of the field trials (Figure 7). At the start of the field trials the phosphorus content of the soil rich in humus was 35 mg P-O^/lOO g soil (DL); on the soil with the lower humus content it was 65 mg/100 g soil (DL). It is likely that on soil (b) the phosphorus displacement was lower, not only because the humus content was lower, but also because the clay content was higher. According to Gooderich and Monke (1971) the P-binding capacity of a sandy loam is four times higher than that of a pure sandy soil. Nevertheless we can state than even on loamy soils considerable amounts of P can be displaced into deeper soil layers, when they are already rich in phosphorus. On loamy soils in 'Stld Wtirttemberg' relatively high amounts of phosphorus were displaced into 60 - 90 cm soil depths, where the P-Oj-content in the top-soil was 110 mg P205/100 g soil (DL) (Figure 8 ) . Seven percent of the total enrichment could be found at 60 - 90 cm soil depth.

-317-

enrichment kg R05/ha (total) 2,7% orq.m. IS input U60kg P205/ha

UOOO ~

in 6 years

3000

5,8Xorg. m.

2000

hS input 2500kg P 0 /ha in 6 years

1000

Fig. 6.

P-enrichment in different ">il depths on hS and loamy sand after 6 years dressing of 90 m pig slurry/ha/year (compared with the unmanured plots).

318-

2 8
OfNf
N
>i

8 8
& c .Cn
o c

M U 3

ft &
c

o
-l

o
A

c c

m u a
in
in
id

(d

u
>i

a>

8
VJ

w
X

R
o
01

R
e> -c

C H P

c a) o

*
10

u
i

!
6
i

ai i 0<

O")

319-

soil depth cm 0

20

100

mg P205/Wg

soil (DL )

20 -

1,0-

60 -

80

100-*

Fig. 8.

P-contents in the soil after different P-enrichment with mineral fertilisers.

C. WILL PHOSPHORUS BE LEACHED IN CONSIDERABLE AMOUNTS INTO THE GROUNDWATER AFTER LONG TERM HIGH SLURRY DRESSINGS? In our investigations of fields with long term high slurry dressings and considerable P-enrichments in the soil, we found only low P-concentrations in the shallow groundwater (2 - 3 m depth) (Table 1 ) . They were no higher than on low or unslurried fields and also no higher than the phosphorus contents in the drinking water. Supposing a leaching rate of 250 mm, the leached amounts of P can be calculated with 0.3 kg P/ha/year. We determined a similar P-leaching in our lysimeter trials and field trials. Slurry dressings of respectively 30 and 60 3 3 m /ha/year in the lysimeter trials, and additionally 90 m slurry/ha/year in the field trials, did not influence the Pleaching. The phosphorus leaching in the humus sands was a
320-

little bit higher than in the loamy sands. contents in the soil were: humus sand (hS)

The average P-

32 mg P_0 /100 g soil (DL), 158 mg P 2 0 5 /100 g soil (total)

loamy sand (IS)

59 mg P 2 0 5 /100 g soil (DL), 164 mg P 2 0 5 /100 g soil (total).

TABLE 1 P-CONTENTS IN THE SHALLOW GROUNDWATER OR DRAINAGE WATER OF HIGH OR LOW SLURRIED FIELDS mg P/l High slurried fields Low slurried fields Unslurried fields Drinking water 0.12 0.12 O.IO 0.12 ) ) ) ca. 0.3 kg P/ha/year

On mineral soils there was no phosphorus movement into the shallow groundwater, although we have determined a considerable phosphorus displacement into deeper soil layers after longterm heavy slurry dressings. On raised bog peat leaching Kuntze and Scheffer water is relatively rich in phosphorus.

(1979) determined P-concentrations in drainage water of 6 - 12 mg P/l, that means 50 - 100 times higher P-concentrations than in our investigations on mineral soils. raised bog peat was 11 kg/ha. After a fertilisation of 160 kg P20j-/ha the leached P20,--amount on The fertilisation of 80 kg Corresponding to Scheffer P_0 5 /ha increased the phosphorus leaching about 1.3 kg P/ha in comparison with unfertilised plots. and Ulrich fix metal ions as chelates. (1960) organic compounds in the soil are able to In this way the organic matter in

soils has a strong influence on the solubility of phosphorus. In acid mineral soils, phosphorus can be precipitated as ironand aluminium-phosphate; in acid peat soils iron and aluminium are fixed by the organic compounds as iron- and aluminiumchelate. Therefore phosphorus cannot be precipitated as iron and aluminium phosphate in these soils.
321-

mg P/l

leached P- amounts in kg/ha

13

-10.7

11

80

160 k g P2 %/ha

F i g . 9.

P - c o n c e n t r a t i o n s in drainage water (average of 1975 - 1978) of r a i s e d bog p e a t a f t e r f e r t i l i s i n g with 0, 40, 80 and 160 kg P-O^/ha as "Thomas-Phosphate 1 . (After Kuntze and Scheffer, 1979)

322-

TABLE 2 P-LEACHING ON hS AND IS IN kg/P/ha/year IN THE FIELD AND LYSIMETER TRIALS WITH DIFFERENT SLURRY APPLICATIONS.

A. Lysimeter experiments m slurry/ha kg P 2 0 5 /ha leaching in kg P/ha/year hS O 30 60 0 140 280 0.41 0.34 0.36 IS 0.12 O.ll 0.11

B. Field experiments m slurry/ha kg P 2 0 5 /ha leaching in kg P/ha/year hS 0 30 60 90 0 140 280 420 0.35 0.63 0.50 0.33 IS 0.48 0.28 0.25 0.35

TABLE 3 P SLURRY AND P-ENRICHMENT IN THE SOIL

Average P,0

content content in soils

20 mg P 0 5 /100 g soil (DL) 60 mg P O./lOO g soil (DL) 40 mg P O /lOO g soil (DL) Respectively 160 mg P_0 /lOO g soil (total) 9 OOO kg P_0 /ha

Recommended limit of the P,0 Difference

Corresponding fertilisation

60 years x 150 (200-50 withdrawal= 150 kg/ha) 25 years x350 (400-50 withdrawal= 350 kg/ha)

323-

On sandy soils with high humus contents in the top-soil, the organic acids can also be responsible for a high solubility of the phosphates and thus for a considerable downward displacement of phosphorus. In deeper soil layers with much lower humus contents and free iron and aluminium ions, the displaced amounts of phosphorus can be fixed, so that we can find here a considerable phosphorus enrichment. This can also be an explanation for our observations, that despite considerable P-displacements into deeper soil layers we could not determine higher P-contents in the shallow groundwater or in the drainage water. It remains to establish in which way the transport of soluble phosphorus into the drainage water is hindered, and if phosphorus is precipitated as iron phosphate before it enters the drainage pipes. D) WHICH PHOSPHORUS ACCUMULATIONS IN THE SOIL LEAD TO A HEAVY PHOSPHORUS DOWNWARD DISPLACEMENT? Apart from acid peat soils, high phosphorus dressings which exceed the requirement of the plants, do not influence the P-contents of the shallow groundwater or drainage water. High phosphorus dressings lead to considerable phosphorus displacements into deeper soil layers. A small P-enrichment of deeper soil layers can be useful for crops, but high Penrichments of deeper soil layers must be considered as wasteful. Under this aspect, it is of interest, which phosphorus enrichments in the soil are acceptable without risk of heavier downward displacements. Our institute gives the recommendation to stop phosphorus fertilisation when the P-contents in the top soil (depending on the humus content) exceed 50, 60 or 70 mg P205/lOO g soil (DL). These limits are a little bit higher than generally named. We gained the experience that in the case of a wet and cold spring we could often observe a phosphorus deficiency, although these fields had received slurry and had a P-content of 70 mg P205/lOO g soil (DL). In low temperatures obviously the availability of slurry phosphate is very low. The efficiency of the slurry phosphates can be

- 324-

improved considerably if part of the total P-requirement is applied with mineral fertilisers. Farms with high slurry production should not exceed the stipulated P-contents in the soil of 50 - 70 mg/100 g soil because a higher P-enrichment in the soil does not improve the plant growth and because high slurry dressings can also have other negative effects for the plants. It is not unusual, after long term high slurry dressings for the soil to become too aerated, so that manganese deficiency occurs. Moreover the exact nitrogen supply will also be more difficult. A phosphorus enrichment of soils in the range from 20 to 60 mg P.,0 /100 g soil, that means an enrichment of 40 mg P 2 5/ 100 g soil (DL) or approximately 160 mg/100 g soil as total P, requires a P-dressing of approximately 9 000 kg P_0,-/ha (Table 3) . Such an enrichment can be reached, when over a period of 60 years, 200 kg P205/ha/year or over 25 years, 400 kg P-05/ha/ year, are applied to the soil. Concerning the requirement of crops such an enrichment does not seem to be very desirable. The efficiency of phosphorus will be better when low amounts of P are applied annually. On soils with normal phosphorus contents approximately 140 kg PjO^/ha/year in the form of slurry are enough to produce optimal yields and to also have a low enrichment effect of topand sub-soil. In comparison to the above examples of the calculated soil enrichment over 60 or 25 years, by this way respectively 4 600 and 6 500 kg PjOr could be saved. At a time, when there is a problem of storage of raw materials, this topic deserves considerable attention.

325

SUMMARY High slurry dressings can cause considerable phosphorus displacements into deeper soil layers. In our trials with Pdressings between 400 and 1 400 kg P 2 0 5 /ha, 8 to 13% of the added phosphorus amounts moved into a soil depth of 60 to 90 cm. We found a faster downward displacement of phosphorus with slurry phosphates than with mineral P fertilisers. The displaced P-amounts increased with increasing P-dressings and with increasing P-accumulation of the soil. The P-downward displacement is particularly high on acid soils with high humus and low clay contents. Although we determined a considerable P downward movement into deeper soil layers, the leached P-amounts into the shallow groundwater or drainage water were very low on mineral soils. On peat soils the P-leaching was high. P dressings, which lead to high P-enrichments of the deeper soil layers, must be considered as waste of phosphorus, because phosphorus in deeper soil layers cannot be utilised by the crops as well as the phosphorus amounts in the top-soil. Adequate utilisation of applied phosphorus is obtained when fields are fertilised annually with maintenance P levels of 140 kg P205/ha.

326-

REFERENCES

Flieg, O., 1935.

U b e r den E i n f l u s s von Humaten auf die B e w e g l i c h k e i t der Zeitsch. ftlr P f l a n z e n e r n . Dtlngung u .

Phosphorsaure im B o d e n . Bodenk. 3 8 ^ 2 2 2 - 2 3 8 .

G o o d r i c h , P.R. and M o n k e , E.J., 1 9 7 1 . saturated s o i l s .

M o v e m e n t of p o l l u t a n t p h o s p h o r u s in

P r o c . I n t e r n . S y m p . on Livestock W a s t e s . Die P h - o s p h a t m o b i l i t a t in A b h a n g i g k e i t Pf l a n z e n e r n . Bodenkunde 1 4 2 , 1 5 5 - 1 6 8 .

K u n t z e , H. and S c h e f f e r , B . , 1 9 7 9 . von der Dtlngung. Zeitsch.

S c h a r r e r , K. and Ktthn, H., 1 9 5 2 .

Sicherversuch zur E r m i t t l u n g der Phosphorsauredtingemittel Z e i t s c h . f. Pf lanzenern.

A u s w a s c h u n g und Tiefenwirkung v e r s c h i e d e n e r allein u n d b e i A n w e s e n h e i t von Stalldtlnger. Dtlngung u . B o d e n k . 58 (103) 1 4 6 - 1 6 2 . Scheffer, U., I960.

H u m u s und Humusdtlngung, Ferdinand E n k e V e r l a g , Stuttgart.

327-

DISCUSSION H. Kuntze (FRG) Figure 9 shows the results of mineral fertiliser treatment over the last three years. The point 0 phosphorus fertiliser means that this part of the trial has not received any phosphorus fertiliser during the last three or four years but prior to that it had been fertilised for several years. In order to provide a better understanding of the topic of this seminar, I have put together some data from another trial where we put slurry on similar high moorland peat soil (Table 1 ) .
TABLE 1 SLURRY ON HIGH MOORLAND

Year

Mineral fertiliser

Pig slurry _, 3 , , , , 3. , 56 m /ha 110 m /ha kg/ha P discharge

Discharge mm

1974/79 Total leachate Average p e r year 21.3 4.3 (0.2-14.5) 38.5 7.7 (1.1-21.4) 86.5 17.3 (2.9-48.8)

817 163
(63-223)

kg/ha N 1974/79 Total leachate Average per year 53.5 10.7 (2.4-27.6)

discharge

63.4 12.7 (4.6-26.3)

122.8 24.6 (11.0-40.5)

^ ^ 1>

80% 10% 10%

NO -N NH-N 4 org-N

-328-

These are soils without any iron or aluminium ions, only organic material. We applied mineral P fertiliser at the rate 3 of 30 kg P/ha/year; 56 m of pig slurry (i.e. approximately 100 kg total-P); and 110 m /ha/year (i.e. approximately 200 kg total-P) . Over a five year period, the average leaching rate of phosphorus was 4 kg P/ha/year, in other words 12% of the phosphoric fertiliser P applied. In the case of the slurries we found 8 to 17 kg P/ha/year leached with the drain water, that means 8% of the total phosphorus applied. It varied between years depending on the discharge rate. Now, the question arises, should we discontinue any fertilisation of these sites? If you change the pH of the soil the decomposition of the organic material would increase too much and then we fear a loss of soil. The real pH of the soil is 4.3; it is a rather acid soil. Since liming will not solve the problem we started new trials some years ago with iron sludges from the aluminium industry, the so-called 'red' sludge, a material which is rich in iron. This material can decrease the amount of soluble phosphorus under these special conditions without decreasing the phosphorus content of the plants. We hope that by applying rates of 10 to 30 t/ha, the danger of excessive phosphorus losses can be decreased. A. Cottenie (Belgium) The most important point is not the quantity being lost in this way but the concentration in the leaching water. R. Unwin (UK) With regard to the 34 fields which you surveyed at the beginning, is the figure of 5.5% organic matter or organic carbon?

329-

H. Vetter (FRG) It is organic matter - under these conditions the carbon content is half that, the C : N ratio of these soils was 28 : 1. R. Unwin Can you tell us the pH of the soils and how they are being cropped - are they arable soils or grassland? H. Vetter These are arable soils, pH 5.3; they are all sandy soils with a very low loam content, not more than 2 or 3%. They are all in the same region where there is a high animal density. H. Kttntze I should add to my earlier comments that the P content of the drainage water in the trial with mineral fertiliser ranged between 5 and 10 ppm. With the low rate of slurry it was between 5 and 14 ppm; with the high rate of slurry, between 5 and 33 ppm. A. Cottenie Thac is very high. The guidelines produced by the European Commission for the quality of soil water in the Netherlands area are 0.4 to 0.7 mg P25 a s the maximum permissible quantities for concentration of phosphorus in soil water. H. Kick CFRG) Professor Vetter talked about the migration of phosphate; I would like to ask how long it takes, if you apply a large amount of slurry, before the phosphate appears a half metre down the profile. Movement might also be a function of leaching and precipitation.

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H. Vetter Some of our results are from 20 years, others, from the field experiments, are from 6 or 7 years. In these experiments we found that if the water content of the soil was very high at the application time, some of the slurry phosphate moved downwards after a few hours. H. Kick Was there also a correlation between the nitrogen content of the water and the phosphate content? H. Vetter In the beginning, yes. A. Suss (FRG) Does the high migration of phosphorus from slurry perhaps depend on the changed physical properties of the soil? H. Vetter Only with regard to a small part; the most important factor for the high migration rate under our conditions is acid soil with high humus content in the topsoil and very little loam. H. Kuntze These drained soils are often damaged by iron clogging. If we apply high levels of slurries, and even of sewage sludges, the iron clogging increases. H. Vetter I would like to ask Dr. Kuntze a question. Is it possible that the phosphate movement in our soils stops immediately before the drain pipes because of the high level of iron? H. Kuntze Well, inside the drain the phosphorus content is higher than outside because of precipitation of phosphorus.
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PHOSPHORUS ACCUMULATION AND MOBILITY FROM LARGE APPLICATIONS OF SLURRY R.J. Unwin Ministry of Agriculture, Fisheries and Food, Great Westminster House, Horseferry Road, London, UK. ABSTRACT Results studies applications were tested. applying no increase are presented up to 25 times Although from seven field trials and four for lysimeter Phosphorus grassland limit, or soil

in which animal manures were applied undesirable 10 times in soil effects grass leachates

to a range of soils. were seen at this resulted or of translocation after 7 upper in little

the maximum recommended levels requirements of poultry

approximately

of phosphorus

below 30 cm years. of to of

in the profile. have not resulted Further studies application the fertiliser could

Very high applications in any extra safely leaching would be required heavy slurry potential of

manure to a sandy

of phosphorus Advisory effort

to determine

how long such rates is directed utilisation full

be sustained. dressings manures.

avoid repeated

by encouraging

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INTRODUCTION Farm animals in the United Kingdom excrete approximately 180 000 tonnes of phosphorus (P) per annum. At current prices this has an equivalent fertiliser value of 60 million sterling assuming a 50% availability for crop growth. An estimated 80 000 tonnes P of the total has to be distributed in various types of manure from housed livestock. To utilise the total NPK fertiliser value of the manures most efficiently and to avoid environmental hazards it is important that they are spread to land at rates which meet crop requirements but minimise leaching and accumulation in soil. The Agricultural Development and Advisory Service (ADAS) of the Ministry of Agriculture Fisheries and Food (MAFF) provides guidance to farmers and growers on these matters. Fertiliser programmes can be drawn up to meet standard recommendations (MAFF, 1979) which incorporate animal' manures to supply all or part of the nutrient requirements of the crops. Whenever manures provide a significant proportion of the applied nutrients farmers are particularly advised to monitor soils and crops to ensure the suitability of the spreading policy. During the last decade ADAS has undertaken a number of studies to investigate the effects of manure applications to a range of soil types, usually under a system of grassland management. Results from seven field experiments and four lysimeter studies are presented in this paper. They allow an assessment to be made of the possible environmental effects of high rates of application and provide information regarding the maximum additions which may safely be applied to agricultural land. EXPERIMENTAL DETAILS AND RESULTS (A) Field Trials Site details and outline experimental treatments for 7 replicated small plot field trials are given in Appendix 1.
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Manure was applied as slurry at varying rates to grassland and compared with inorganic fertiliser controls which usually received 375 kg/ha N per annum plus phosphorus and potassium according to soil analysis. Four trials tested pig slurry and three cow slurry. Slurry treatments were applied for 2, 3 or 4 years usually during the winter period. Of the many aspects studied only results pertaining to phosphorus are given here. Slurry and grass samples were analysed for total P to permit a P balance to be determined. Available P (sodium bicarbonate extractable, after Olsen et al., 1954; MAFF, 1973) was determined on soils at the end of each experiment. Grass was cut by autoscythe 3 - 6 times per season according to growth. The highest rates of slurry depressed grass yield at some stage of each trial. The plots at site 4 were reseeded after 2 years' application and this allowed a study of residual effects on plots to which no further slurry was applied. Effects on herbage composition Phosphorus content of herbage was raised by cow slurry application at all sites. Details are given in Table 1 a - c. On the medium textured soils at Sites 2 and 3 application of slurry P in excess of 165 kg/ha/annum caused no further increase in herbage P content. By contrast on the more acid poorly drained heavy textured soil (site 4) increases above control levels were not observed until annual applications reached 378 kg/ha P. This pattern of results was confirmed by results with pig slurry (not given in detail here). There was no evidence of a differential uptake of phosphorus from the different sources of slurry. The results from site 4 suggest that two years after slurry application ceased uptake by the grass was no greater than on control plots although 'available' soil residues remained high. Moisture stress and low nitrogen availability will have accentuated this effect.
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TABLE 1 SLURRY AND PHOSPHORUS APPLIED AND THE EFFECT UPON PHOSPHORUS CONTENT AND CALCIUM : PHOSPHORUS RATIO IN HERBAGE (MEAN OF ALL CUTS)

r
a) Cow slurry. Site 2 Bridgets Experimental Husbandry Farm (EHF) 4 years

Total slurry m3/ha Total P kg/ha % P in herbage DM Ca : P in herbage DM

Nil 101+ 0.28 2.57

844 254 0.33 1.94

1 688 508 0.34 1.68

3 376 1 016 0.36 1.61

b) Cow slurry. Site 3b. Trawsgoed EHF. 4 years 3 Total slurry m /ha Total P kg/ha % P in herbage DM Ca : P in herbage DM

Nil 179+ 0.36 2.17

1 200 663 0.41 1.63

2 400 1 326 0.43 1.47

4 800 2 652 0.42 1.34

c) Cow slurry. Site 4b. Cloford Manor.

2 years + 2 years residual study

Total slurry m /ha Total P kg/ha % P in herbage DM Ca : P in herbage DM % P in herbage 2 years after slurry application ceased

Nil 189+ 0.39 1.69 0.28

292 246 0.40 1.25 0.26

584 492 0.39 1.31 0.24

810 757 0.39 1.20 0.26

1 620 1 514 0.50 1.04 0.29

+ from inorganic fertiliser

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The optimum concentration of phosphorus in forages for dairy cows and pregnant ewes is O.40to0.50% (ADAS, 1975). By raising herbage P content high rates of slurry improved this aspect of herbage quality. However other mineral levels were adversely affected. Potassium and nitrate-nitrogen was often high and sodium levels were depressed, particularly by cow slurry. The high potassium levels in the soil/plant system also depressed calcium in the herbage. The ratio of Ca : P in herbage should ideally be between 1.0 : 1.0 and 1.5 : 1.0 for grazing ruminants. Slurry applications had beneficial effects in reducing Ca : P ratios closer to this standard without reducing absolute calcium values to disturbingly low levels. Seasonal variation usually resulted in greater Ca differences than slurry treatments. Effects on soil_hosghorus_reserves At sites 1, 2 and 3 plots were sampled to a maximum 30 cm depth, whilst site 4 was sampled incrementally to 90 cm. The proportion of the P balance detected as available soil P varied with type of slurry and rate of application. At low rates of pig slurry (409 kg/ha P applied) up to 40% of the balance could be accounted for, but only 10% at high rates (5 869 kg/ha P ) . By contrast recoveries of cow slurry P were always less than 13% and rate of application apparently had no effect on the rate of recovery. Depth sampling at site 4 indicated no increase in available P below 30 cm when 1 514 kg/ha cow slurry P were applied over two consecutive winters. However, when pig slurry was applied in each month for 4 years to give total P applications up to 5 689 kg/ha increases in available P were noted at 90 cm (Table 2). However of the increase in available P, 94% was retained in the surface 30 cm. Consideration of copper analyses suggested that movement of whole slurry had taken place to depth, probably in dry summer conditions.

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TABLE 2 SODIUM BICARBONATE EXTRACTABLE P TO DEPTH IN SOIL AFTER SLURRY APPLICATION. SITE 4 CLOFORD MANOR

(a) Cow slurry

4 year Total P application kg/ha Depth of sample cm Control 189+ Slurry 492

246

757

1 514

Extractable P mg/1 0 - 5 5-15 15 - 30* 30 - 45 60 28 10 4 32 20 10 4 45 32 12 3 62 47 13 3 78 70 17 3

(b) Pig slurry

4 year Total P application kg/ha Depth of sample cm Control 189+ Slurry 742

255

2 295

5 636

Extractable P mg/1 0 - 5 5-15 15 - 30* 30 - 45 45 - 60 60 - 75 75 - 90 60 28 51 32 16 4 1 2 3 121 82 29 5 4 4 4 209 178 82 18 7 5 6 288 252 92 7 10 8 9

io
4 4 3 2

* All plots were cultivated to 20 cm when more than half of the slurry had been applied. + As inorganic fertiliser.

338-

(B) Lysimeter studies 1) Pig slurry^-^ewcastle Experimental details and nitrogen leaching results for a 3 year lysimeter experiment were reported by Hewgill and Le Grice (1976). Information on phosphorus translocation is now available from this study. Six hundred m /ha per year of slurry with 7 - 9 % dry matter content were applied either in winter or summer to a light loamy sand soil which was either kept fallow or cropped with grass. Time of application had no effect on translocation but movement appeared greater in the absence of a growing crop when quantities of leachates increased. Despite P applications up to 1964 kg/ha, total soil phosphorus had not increased significantly below 30 cm by the end of the experiment.
TABLE 3 TOTAL S O I L PHOSPHORUS AT CONCLUSION OF THREE YEAR LYSIMETER STUDY WITH P I G SLURRY

Slurry treatment and 3 year tot il P application kg/ha Depth of sample cm Nil 273+ Summer-grass 1964 Winter-grass 1094 Summer-fallow 1316

Total soil P mg/kg Surface Mat 0 - 5 5-15 15 - 30 30 - 45 45 - 60 690 474 500 359 244 180 9 070 1 547 649 391 128 81 8 840 1 298 503 393 240 172 1 620 600 542 302 149

+ As inorganic f e r t i l i s e r The q u a n t i t y of P d e t e c t e d i n t h e l e a c h a t e s i n c r e a s e d w i t h r a t e of s l u r r y b u t o n l y t o a maximum e q u i v a l e n t t o 0 . 0 3 k g / h a P per year at the highest a p p l i c a t i o n . The mean P c o n c e n t r a t i o n i n l e a c h a t e s f o r t h i s t r e a t m e n t was 0.113 mg/1 ( r a n g e 0.009 t o 0 . 9 9 0 mg/1 SD 0 . 2 4 0 ) .

339

2) Cow slurrY_-_Newcastle A six year experiment under similar conditions simulated an intensive cattle grazing regime. Dung and urine (30 kg/ha P) In the were applied annually with or without high rates of inorganic fertiliser including 78 kg/ha P as super phosphate. final year leachates were analysed for orthophosphate-P. Losses were equivalent to 0.86 kg/ha P per annum in the absence of effluent and 0.3 6 kg/ha where dung and urine had been applied. 3) Cow slurry I_ Br .i st 2l Upto 270 m /ha equivalent of cow slurry (5 to 7% dry matter) has been applied annually for six years to a sandy loam soil and to a chalk profile (30 cm of calcareous silty loam over tightly packed chalk rubble). Eight hundred and fifty kg/ha P have Only trace quantities of probably been applied in this time. due to slurry has been observed. 4) Poultryjnanure -_Gleadthorp_e Exgerimental_HusbandrY_Farm Since 1973 up to 75 t/ha of manure from a battery unit has been applied annually to a sandy soil in lysimeters and a range of arable crops grown. Table 4 indicates results of P leaching Total quantities of P leached at for the last three seasons.

phosphorus have been reported in the leachates and no increase

the highest rate of application remain less than 0.3 kg/ha. Concentrations of P in these leachates are less than from the control (no fertiliser or manure). in future seasons. It remains to be seen if the apparent trend for increasing concentrations is maintained

340-

TABLE 4 RESULTS OF A LYSIMETER STUDY APPLYING POULTRY MANURE TO A SANDY SOIL. LAST 3 YEARS DATA OF A STUDY COMMENCED IN 1973 Total P applied (kg/ha) Crop Highest rate Total P leached (kg/ha) Highest rate THE

Mean concentration P in leachate mg/1 Highest rate 0.032 0.042 0.073 Control

1977 spring barley 1978 potatoes 1979 spring barley

442 1 031 371

0.13 0.09 0.27

(0.041) (0.067) (0.107)

SUMMARY AND CONCLUSIONS Field trials with cow and pig slurry have shown that high rates of slurry can improve the phosphorus content of herbage for grazing stock but that this benefit is more than counteracted by the adverse effects of other nutrients. The uptake of phosphorus by herbage from cow and pig slurry was similar, but soil type affected the availability to the growing plant, and residual effects on heavy soils may be shortlived. Phosphorus residues in soil from pig slurry applications appear to be more readily extractable with sodium bicarbonate than those from cow slurry. Extractable P increases rapidly in surface soil when manure loadings exceed crop requirements. On a heavy soil no increase in extractable soil P was detected below the depth of incorporation when 757 kg/ha P was applied as cow slurry for each of two consecutive winters. This quantity of P is equivalent to that excreted by 112 dairy cows housed for a six month period. When pig slurry was applied throughout the year to the same soil no significant increase in extractable P was detected below the depth of incorporation when 185 kg/ha was applied for each of four years. This quantity of P is equivalent to that excreted by 104 mature bacon pigs in 12 months. When this rate of application was increased by a factor of 3 and of 9 small
- 341-

increases of P were detected to 90 cm. It is believed much of this accumulation to depth resulted from mass movement of slurry when the soil dried and cracked in summer. Lysimeter studies with pig slurry on a light sandy soil detected only very small extra leaching losses (0.02 kg/ha P/ annum) when 654 kg/ha P were applied for three consecutive years. (Equivalent to the manure from 366 pigs). No increase of total phosphorus was detected below 30 cm in the presence of a grass crop. An average application greater than 600 kg/ha P/annum applied as poultry manure to a sandy soil under arable cultivation for 7 years has resulted in no increase of P leaching compared to the nil P treatment. These results indicate that even when slurry is applied to soil at annual rates which supply phosphorus considerably in excess of crop requirements the environmental impact can be minimal. However further work is required to ascertain the long term effects of excessive applications when the soil's ability to retain applied phosphorus might eventually be exceeded. With the increasing cost of artificial fertilisers the application of repeated high rates of manure would seem unlikely and advisory work is directed to encourage utilisation of the nutrients. It must be remembered that when large single applications of slurry are applied under adverse soil conditions (very wet or very dry) significant translocation can occur to depth in soil and also to water courses. The understanding and co-operation of farmers is required for them to adopt responsible landspreading policies which will prevent environmental hazards. ACKNOWLEDGEMENTS The work reported here was undertaken over a period of 10 years by ADAS. I extend my thanks to Regional Soil Science colleagues and the Directors and staff of the Experimental Husbandry Farms for permission to use their data, most of which has not been previously published.

342-

REFERENCES ADAS, 1975. The important mineral elements in animal nutrition and their ADAS Advisory Paper No. 16, MAFF In

optimum concentration in forages. (Publications), Pinner, Middlesex. Hewgill, D. and Le Grice, S., 1976. HMSO (London).

Lysimeter study with pig slurry.

Ministry of Agriculture, Fisheries and Food.

Technical Bulletin, 32. US Dept. Agric.

Olsen, S.R., Cole, C.V., Watanabe, F.S. and Dean, L.A., 1954. Circular No 939. MAFF, 1973. 27. MAFF, 1979. The analysis of agricultural materials. HMSO (London). Fertiliser recommendations. GF 1.

Technical Bulletin,

HMSO (London).

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APPENDIX 1 - SUMMARY OF FIELD TRIAL SITES AND TREATMENTS

Site

Trials/year

Annual average rainfall mm

Soil texture drainage Clay loam over Boulder Clay Brickfield series Imperfectly drained pH(water) a) 5.1 b) 5.9 Clay loam over Clay-with-flints over chalk Winchester Series Moderately well drained pH 6.8 Stoney sandy loam

Soil samples taken to 0 - 75 mm 75 - 150 mm 150 - 300 mm (by Auger)

Treatments Control - 57 kg/ha P Slurry equivalent to 155 pigs/ha 465- " " Control - 33 kg/ha P Slurry equivalent to 75 pigs/ha 155 " " 310 " " Control - 25 kg/ha P Slurry equivalent to 5 cows/ha 10 " 20 "

Great House Experimental Husbandry Farm (EHF) Lancashire (NW England)

a) Pig

1969-1971

1 100
b) Pig 1970-1972

Bridges EHF Hampshire (S England) Trawsgoed EHF Dyfed (W Wales)

Cow 1970-1973

750

0 - 150 mm (Auger) 0 75 mm

a) Pig

1970-1971

Control - 44 kg/ha P Slurry equivalent to

Control - 44 kg/ha P Slurry equivalent to

1 250
b) Cow 1970-1973

Rheidol Series Well drained pH a) 6.4 b) 5.9 Silty clay loam over silty/sandy clay Denchworth series Poorly drained pH a) 5.3 b) 5.3

75 - 150 mm (Auger)

83 pigs/ha 166 " 333 M

5 cows/ha 10 " " 20 " "

Cloford Manor, Somerset (SW England)

a) Pig

1972-1976

850 b) Cow 1972-1976

0 - 50 mm 50 - 150 mm 150 - 300 mm 300 - 450 mm etc. to 900 mm (By motor driven corer)

Control - 47 kg/ha P Slurry at 8 mm Applied in per annum 24 mm 12 monthly applica72 mm tions through year 216 mm Control - 47 kg/ha P Slurry at 12 mm JApplied in per annum 24 mm J12 monthly applica47 m m M t i o n s through 96 mm ^winter

DISCUSSION
H . Tunney (Ireland)

In one of your Figures you showed availability of 50% for phosphorus in slurry, 60% in farmyard manure. I have seen those figures many times. What do you base these figures on for advisory work? R. Unwin (UK) Mr. Williams made the comment when referring to sewage sludge yesterday that the 50% availability for sewage sludge was based on a small amount of evidence and I suggest that it is likewise for these figures. I do not wish to place too much emphasis on them for the future because I do not believe that they are all that relevant to our situation of non-responsive manuring for phosphate, where we are attempting to maintain P levels in the soil. D. Sauerbeck (FRG) As far as your figures on the influence of sewage sludge on the phosphorus content in the herbage are concerned, do you not think that the tremendously different amounts of nitrogen being applied with increasing doses of sludge, and, of course, the change in the whole plant association, will completely blur or supersede the direct influence of sewage sludge phosphorus? R. Unwin Yes, I feel that is right. The picture I would draw from this is the overall effect of the dressings. I would say that the conditions were relative to different sites. One could perhaps say that we were seeing differences on the soils but I could not substantiate them to any great extent. Certainly, I referred to the effect of the very dry season on phosphorus but I feel there was an effect of nitrogen there as well because we had less nitrogen supply from manures applied two years previously as well.

345-

H. Kick (FRG) Did you also underline the depressed calcium content of the herbage coming from the high potash supply? What was the content of potash reached in your herbage? Magnesium is also a very important factor in this context. R. Unwin I think the maximum potash was just over 6%, 4 to 5% would be the normal situation. With regard to magnesium, the high dressings tended to have a smaller effect on the magnesium content than we expected. They tended to be low throughout because the data I was presenting referred to Italian ryegrass swards, which, typically for that soil, only have 0.1 to 0.15 mg/kg magnesium. The depression of sodium content was much more marked than the depression on magnesium.

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MOBILITY OF PHOSPHORUS FROM PIG SLURRY IN SOILS R.G. Gerritse Institute for Soil Fertility, Haren, The Netherlands.
ABSTRACT Phosphorus phosphorus. soil solution mobility in soils will not only be due to part of phosphorus bound (mainly 6:1. part It phosphorus. orthophosphate) Only in fresh the apparent of organic phosphorus to soil. through no and slurries equilibin to amounts origin, With the organic and orthophosphorus by all added high soil inorganic in the

More often

than not the greater

is made up of organically contains both inorganic

Pig slurry organic phosphorus

in the ratio be found,

of roughly rapidly

can much lower ratios rium value pig slurry 1% of total appears

approaching organic

of 6 : 1 on ageing. to be mobile. weight only,

Only a small This mobile

phosphorus

P or 10 - 20 mg P/l pig slurry. and is only slightly this fraction could

is of microbial to migrate rainfall, retained

of high molecular doses of pig slurry fairly leaching phosphorus are rapidly phosphate phosphorus rapidly.

absorbed

appears

With normal doses under average be detected. are strongly cycle.

significant

of P in this fraction taken

The remaining The mobility by considering of mainly

compounds in pig slurry with pig slurry orthophosphate.

in the soil

up in the phosphorus quite

added to soils as

can be said

to be governed

and can be modelled

adequately

347-

PHOSPHORUS COMPOUNDS IN PIG SLURRY In pig slurry 10 to 20% of total P is contained in organic P compounds. Analysis data for various P compounds in pig slurry are given in Table 1 (Gerritse, 19 77) . In fresh slurry the organic P content can be very high (up to 1% of dry matter), mainly due to the presence of inositolhexaphosphate (IHP) and adenosinetriphosphate (ATP) (Gerritse, 19 78). Both IHP and ATP decrease rapidly and are practically negligible after 5 to 6 months storage at 15 to 20 C. Dissolved inorganic- and organic P in pig slurry are rapidly converted into each other by the action of micro-organisms. From the measurements of 32 PO. distribution rates in pig slurry it follows that complete turn-over of dissolved inorganic P through micro-organisms takes place in about 10 to 20 weeks, giving a microbial turn-over rate of about 10 mg P/week/1 average slurry (Gerritse and Zugec, 1977). Analysis of gel filtration fractions of pig slurry solution indicates that the dissolved organic P compounds are related to polydeoxyribonucleotides (DNA) and have a high molecular weight (Gerritse and Eksteen, 19 78) . Mineralisation rates of organic P in pig slurry can vary greatly and are influenced by aeration, storage time, dry matter content and temperature. Results of following the organic P contents of various pig slurries with storage time are shown in Table 2. The concentration of dissolved otganic P was in all cases unaffected by storage time and remained constant at 10 to 20 mg P/l. From Table 2 it can be said that for pig slurry stored between 1 week and 1 year, mineralisation rates of organic P will lie between 0 and 20 mg P/week/1 slurry, increasing with decreasing aeration. The corresponding rates for loss of organic matter are 3 toO.l g/week/1 slurry, decreasing with decreasing aeration.

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TABLE 1 DISTRIBUTION OF PHOSPHORUS AMONG ORGANIC AND INORGANIC PHOSPHORUS COMPOUNDS IN PIG SLURRY P content: (% o f DM) 2 0.3 0.2 0.1 0.04 0.1 0.03 Average o f t o t a l P (%) 85 15 5 2 1.5 1 1

Total Total

inorganic organic P in P

1.5 0.2

Inorganic

solution hexaphosphates (IHP)

0.01. 0.01 0.02 (ATP)

P in inositol P in

micro-organisms

P in adenosine-5-triphosphate Organic P i n solution

O.OOO 0.01 -

Ten slurries were analysed. Dry matter content ranged from 5 to 10% and time of storage from 1 to 6 months.

TABLE 2 ORGANIC PHOSPHORUS (P ) AND DRY MATTER ORG FUNCTION OF TIME OF STORAGE (DM) CONTENTS OF PIG SLURRY AS A Slurrv DM tr,\ P 4

Storage (weeks)

time:

Slurry DM (g)

1 P org (mg)

Slurrv DM (g) P

2 org (mg) DM (g)

Slurrv P org (mg)

o r g

(g)

(mg)

0 1 3 6 7 10 16 18 21 63 132

74 73

280 210

63.5t

400

68 67

160 150

66 59.5

200 200

57.7tt

75

67

130

62.6 60.5 55.3

150 140 110

T

51.2 39.9

200 200

63 8 61. 5

80 80

34.

7ttt

70

torganic matter=73.2%(of D M ) ; ttorganic matter=65.8%;tttorganic matter=60.9% Pig Slurries 1 and 2 were stored in closed containers, relieving pressure when necessary. Slurry 3 w a s stored in a wide-necked open container. Slurry 4 , identical to Slurry 3, w a s aerated and agitated during storage. Data are related to 1 kg slurry at time = 0. 349-

SOIL FIXATION Pig production in the Netherlands is particularly intensive in the sandy soil regions. Pig waste in the form of slurry with a dry matter content of 5 to 10% is sometimes dumped on soils at rates of 100 and more tons/ha/year. Under average conditions a strong fixation of inorganic P in soils can be expected. The main factors affecting this fixation appear to be: Fe, Al and Ca content of the soil, specific surface area, pH and redox potential. Time is also an important parameter. After an initial rapid adsorption, fixation of inorganic P in soils increases slowly with time due to chemical immobilisation reactions with rate constants of the order of (months) / (years) . The rate of adsorption of inorganic P from pig slurry solution in sandy soils has a maximum at a pH of about 5 (Figure 1 ) .

% inorganic P adsorbed 70r 60 50 40 30 20 10 0 1

Fig. 1.

9 pH

Fraction of inorganic P in pig slurry solution, obtained after centrifugation at 40 OOO G for 30', adsorbed to soil after 24 h. Ten g soil was equilibrated with 40 ml slurry solution at different values of pH. -350-

The a d s o r p t i o n was measured a f t e r 24h e q u i l i b r a t i o n of 10 g s o i l w i t h 40 ml s l u r r y s o l u t i o n . A p p a r e n t l y t h e H-PO. i o n of which t h e c o n c e n t r a t i o n i s a t a maximum a t pH 5 i s t h e r a t e determining i o n . Organic P d i s s o l v e d in pig s l u r r y i s o n l y m e a s u r a b l y a d s o r b e d i n sandy s o i l s w i t h v a pH of l e s s t h a n 5 ( F i g u r e 2 ) . O r g a n i c P i n p i g s l u r r y s o l u t i o n can t h u s be much more m o b i l e i n t h e s o i l t h a n i n o r g a n i c P . O r g a n i c P forms an i m p o r t a n t p a r t of t o t a l s o i l P . I n t h e s u r f a c e h o r i z o n of s o i l s 10 t o 80% of t o t a l P can be c o n t a i n e d i n o r g a n i c compounds. The l a r g e r p a r t of t h i s s o i l o r g a n i c P i s i n p h y t a t e s , which a r e F e , A l , Ca and Mg complexes of m y o - i n o s i t o l h e x a p h o s p h a t e (IHP). High m o l e c u l a r w e i g h t complexes c o n t a i n i n g IHP and o t h e r o r g a n i c P compounds have a l s o been found i n s o i l s o l u t i o n . Most o r g a n i c P compounds i n t h e s o i l can be u t i l i s e d by p l a n t s and m i c r o - o r g a n i s m s e i t h e r d i r e c t l y o r a f t e r d e g r a d a t i o n . P h y t a t e s , however, e s p e c i a l l y Fe and Al p h y t a t e , a r e v e r y p e r s i s t a n t i n t h e s o i l and a l m o s t u n a v a i l a b l e t o p l a n t s and micro-organisms.
ppm o r g a n i c P i n s o l u t i o n 25

slurry si u r r y 4- soi I

9 pH

F i g . 2.

Adsorption of o r g a n i c P from p i g s l u r r y s o l u t i o n t o s o i l under the same c o n d i t i o n s as given in F i g . 1. -351-

In Table 3 results are shown of the calculation of some possible contributions to the IHP content of a sandy soil (Gerritse, 1978) . A steady increase of soil phytate can be expected if it is assumed that all IHP contributed is bound and only slowly decomposed. In this respect it would be interesting to measure the age of soil phytate through its 14C content. The contribution of soil micro-organisms to phytate P is difficult to estimate. Sometimes, e.g. in the case of Phragmites (sommon reed), large amounts of IHP are produced in the rhizosphere under eutrophic conditions.
TABLE 3

PHYTATE ( I H P ) CONTENT OF THE SURFACE HORIZON OF A PODZOL S O I L AND SOME POSSIBLE SOURCES OF IHP ACCUMULATION. TOTAL AMOUNTS OF INORGANIC AND ORGANIC P INVOLVED ARE ALSO G I V E N .

p Soil layer (0 - 20 cm) 100 tons of pig slurry /ha Dead grass roots/year Dead worms/year

IHP

P. inorganic 900 kg/ha 75 - 200 1.9 - 6.2 0.2 - 3.5

P organic 600 kg/ha 10 - 30 1.6 - 5.2 0.5 - 6.7

150 kg/ha 0.5 0.2 - 10 - 0.65

0.01 - 0.2

DECOMPOSITION OF ORGANIC P UNDER STATIC CONDITIONS T h i s was i n v e s t i g a t e d in the following experiment. a reclaimed pig slurry pig + + Three

b a t c h e s of 1 kg of t h e s u r f a c e h o r i z o n of ( r o u g h l y e q u i v a l e n t t o a t r e a t m e n t of slurry/ha). s l u r r y m i x t u r e was a b o u t different temperature (2, 2.

podzol

w e r e a i r d r i e d a n d m i x e d w i t h 50 g f r e e z e - d r i e d W a t e r was t h e n a d d e d u n t i l for

500 t o 1 000 t t h e pF o f

the s o i l of s o i l a

The r e s u l t i n g b a t c h e s

s l u r r y were then incubated kept constant. with the neutral conditions b a t c h e s of

12 m o n t h s , e a c h b a t c h a t t h e same s o i l w e r e

20 a n d 30 C ) .

The w a t e r c o n t e n t was treated same three in c.

Three b a t c h e s of sodium s a l t

o f IHP a n d k e p t u n d e r t h e

as the s l u r r y

treated soils.

I n t h e same way 4 a , b and

u n t r e a t e d s o i l s were used as c o n t r o l s .

Changes

P , N, o r g a n i c m a t t e r a n d pH a r e shown i n T a b l e s
-352-

At 30 C organic P from pig slurry added to the soil appears to be almost completely mineralised after 1 year, while at 20 C roughly 40% and at 2 C roughly 20% is mineralised after 1 year. IHP, when added as neutral salt, is apparently not decomposed at all under the conditions of the incubation experiment. In the untreated soil the decomposition of organic P is in the region of a few %, amounting to about 1 mg P/l soil solution/ week. Phosphatase activities were also measured in the incubated batches of soil from the decomposition rate of added p-nitrophenylphosphate (Gerritse and v. Dijk, 1978) . MichaelisMenten kinetics applied reasonably well. Results are given in Table 5. The enzyme concentration (proportional to V ) starts max to increase after about 30 weeks in pig slurry only. In all other cases K and V do not appear to change significantly, although with pig slurry the K is significantly greater, indicating an inhibition effect.
TABLE 4a RESULTS OF THE ANALYSIS OF A SANDY TOPSOIL INCUBATED AT VARIOUS TEMPERATURES FOR 12 MONTHS. THE pF OF THE SOIL WAS KEPT BETWEEN 1 AND 2. Time (weeks) 4 4 4 13 13 13 30 30 30 54 54 54 T P inorg P org

C
2 20 30 2 20 30 2 20 30 2 20 30

%
0.033 0.033 0.034 0.035 0.035 0.035 0.035 0.034 0.035 0.034 0.035 0.036

%
0.028 0.028 0.026 0.027 0.027 0.028 0.024 0.027 0.023 0.026 0.026 0.026

Organic matter %
6.0 6.0 6.0 6.1 5.9 6.0 6.2 6.1 5.9 6.2 5.9 5.7

pH (H 2 0)

N Kjeldahl

%
0.17 0.16 0.16 0.16 0.16 0.15 4.6 4.5 4.6 4.6 4.5 4.6 0.16 0.16 0.16 0.15 0.15 0.14

353-

TABLE 4b RESULTS OF THE ANALYSIS OF A SANDY TOPSOIL INCUBATED AT VARIOUS TEMPERATURES AFTER MIXING WITH PIG SLURRY. THE pF OF THE SOIL WAS KEPT BETWEEN 1 AND 2. Time T (weeks)
4 4 4 13 13 13 30 30 30 54 54 54

P inorg

P org

C
2 20 30 2 20 30 2 20 30

Organic matte r

N+ Kjeldahl

V,,
%
0.005 0.055 0.041 0.019 0.076 0.056 0.060 0.079 0.068 0.062 0.081 0.066

pH (H 2 0)
4

%
0.094 0.095 0.094 0.096 0.102 0.105 0.095 0.100 0.106 0.097 0.099 0.107

%
0.04 0.04 0.04 0.04 0.035 0.03 0.045 0.04 0.03 0.04 0.04 0.03

%
9.6 8.6 8.2 8.7 8.3 7.8 8.9 8.3 7.6 8.6 7.8 7.0

%
0.31 0.29 0.28 0.30 0.26 0.25 0.26 0.23 0.20 0.26 0.25 0.20

%
0.05 0.01 0.025 0.05 O.OOl 0.01 0.15 0.000 0.005 0.012 O.OOl 0.017
5.0 4.5 4.8 5.0

2 20 30

4.45
5.0

t Kjeldahl determinations were done without addition of salicylic acid, thus giving interference by NO . TABLE 4c RESULTS OF THE ANALYSIS OF A SANDY TOPSOIL INCUBATED AT VARIOUS TEMPERATURES AFTER MIXING WITH INOSITOL HEXAPHOSPHATE. THE pF OF THE SOIL WAS KEPT BETWEEN 1 AND 2. Time (weeks)
T P P

inorg

org

C
4 4 4 13 13 13 30 30 30 54 54 54 2 20 30 2 20 30 2 20 30 2 20 30

%
0.027 0.029 0.028 0.029 0.028 0.028 0.029 0.030 0.028 0.028 0.027 0.029

%
0.120 0.120 0.120 0.115 0.120 0.120 0.120 0.130 0.125 0.125 0.127 0.128

Organic matter

pH(H 2 0)

Kjeldahl

%
0.17 0.15 0.17 0.16 0.14 0.16 0.17 0.16 0.16
5.8 5.5 5.4

6.3 6.2 6.2 6.3 6.3 6.3 6.3 6.1 6.2 6.2 6.0 6.0

0.16 0.15 0.14

-354-

TABLE 5 MICHAELIS-MENTEN RATE CONSTANTS OF ACID PHOSPHATASE A C T I V I T I E S OF A SANDY TOPSOIL INCUBATED AT VARIOUS TEMPERATURES FOR 1 2 MONTHS WITH AND WITHOUT ADDITION OF INOSITOL HEXAPHOSPHATE OR P I G SLURRY. THE p F OF THE S O I L S WAS KEPT BETWEEN 1 AND 2 . K m in pmoles/1; V max in ymoles/1/g/h. K V

max

nax

max

4 week soil:

13 weeks

30 weeks

54 weeks

2C 20 30
soil + phytate:

70 50 60

110 100 90

50 75 100

80 80 80

60 65 80

75 70 90

80 80 80

85 85 95

2C 20 30
soil + slurry:

60 60 40

100 85 70

90 70 80

90 85 60

100 70 70

80 75 75

50 75 70

75 90 85

2C 20 30

loo
90

90

130 110 75

lOO 90 105

85 90 90

100 160 145

95 220 200

160 105 180

150

2 35

370

After 54 weeks the s o i l s were sampled and e q u i l i b r a t e d with water i n the r a t i o 45 g s o i l : 60 ml water for 24 h o u r s . After c e n t r i f u g a t i o n a t 40 000 G during 30 mins. the supernatant was analysed for organic and inorganic P. As can be seen from the r e s u l t s i n Table 6, enormous differences in water e x t r a c t a b i l i t y of P are caused by the various t r e a t m e n t s . The low concentrations of organic P in the case of s o i l + s l u r r y coincide with a high l e v e l of enzyme a c t i v i t y . The high concentration of inorganic P, both in the s o i l + s l u r r y and i n the s o i l + IHP, i s most l i k e l y due to competitive adsorption with subsequent displacement of inorganic P. The high concentration of organic P i n the s o i l + IHP i s a l s o probably due to displaced s o i l organic P.

355

TABLE 6 P ANALYSES OF THE SOLUTIONS OBTAINED AFTER SHAKING THE SANDY TOPSOILS INCUBATED WITH INOSITOL HEXAPHOSPHATE AND P I G SLURRY WITH WATER. A RATIO OF 4 5 g S O I L : 6 0 ml WATER WAS USED. THE SOLUTION WAS CENTRIFUGED AT 4 0 OOO G FOR 3 0 M I N S . THE ANALYSES WERE MADE AFTER 5 4 WEEKS OF INCUBATION.

Total P mg/1 soil: 2C 20 30 soil + phytate: 2C 20 30 soil + slurry: 2C 20 30 0.188 0.145 0.226

Inorganic P mg/1 0.122 0.109 0.106

Organic P mg/1 0.066 0.036 0.120

9.44 5.69 4.11

5.22 3.18 2.61

4.22 2.51 1.50

11.35 7.66 4.60

10.4 7.65 4.60

0.95 0.01 O.OO

DECOMPOSITION OF ORGANIC P UNDER DYNAMIC CONDITIONS S a n d y s o i l s w e r e c o r e d t o a d e p t h o f 1 0 0 cm i n c y l i n d r i c a l 2 p e r s p e x t u b e s ( c r o s s s e c t i o n a l a r e a 1 1 3 cm ) . The t o p 10 cm o f the soil column was m i x e d w i t h 77 g f r e e z e - d r i e d 1 000 t / h a . pig flow slurry was the through ( e q u i v a l e n t t o a t r e a t m e n t of about column was a t e q u i l i b r i u m . for inorganic activity. After Rainfall

s i m u l a t e d a t a r a t e of 1 cm/day such t h a t w a t e r The c o l u m n e f f l u e n t a n d o r g a n i c P , N, p H , c h l o r i d e Some e f f l u e n t 3. of p i g s l u r r y

was m o n i t o r e d soil

and p h o s p h a t a s e column cenas

a y e a r t h e p e r c o l a t i o n was s t o p p e d and t h e d a t a of a podzol s o i l solution, obtained

analysed in layers. a r e shown i n F i g u r e treated with 1 l i t r e trifugation at

I n a n o t h e r e x p e r i m e n t a s i m i l a r s o i l was after subsequently Effluent 3 and 4 spite

40 0 0 0 G, a t a r a t e o f 1 c m / d and

p e r c o l a t e d w i t h w a t e r i n t h e same way a n d a t t h e same r a t e was done f o r t h e column t r e a t e d w i t h d r i e d s l u r r y . data are given in Figure 4. As c a n b e s e e n from F i g u r e s

t h e only mobile P appears t o be d i s s o l v e d o r g a n i c P, i n

356-

m g P/liter 1.5 P organic

m g Cr/liter 1500r

VP/VQ

1000-

500

100

1
Fig. 3.

10

1 1

12

13 U Ve/VQ

Effluent data for a reclaimed 'haar' podzol soil column. Rainfall in the column was simulated at a rate of 1 cm/d. Volumetric water content of the column (V0) was 2.8 1. The top 10 cm of the column was mixed with dried pig slurry (70 g ) . 357-

P/liter

11
Fig. 4.

12 13 U v e /v 0

Effluent data for a reclaimed 'haar' podzol soil column. The column was treated with 1 litre of slurry centrifugate instead of dried pig slurry. Other conditions as in Figure 3. 358-

' r organic 0.03 0 04

0/ p

tf
/ / / / / ;
I 40

/ 0

4.5 '

1 (2

5 '

pH-KCI 5 ~1
--* l

20

/ )

\\

\ i/

60

Y 1 lj i

80 cm depth

Fig. 5.

R e s u l t s of a n a l y s e s of s o i l columns of a r e c l a i m e d ' h a a r ' podzol w i t h o u t (O) , a n d w i t h a d d i t i o n o f d r i e d p i g s l u r r y (2) o r s l u r r y c e n t r i f u g a t e ( 1 ) , a f t e r 1 y e a r ( t o t a l e f f l u e n t volume = 3 9 . 5 1 ) . 359-

of the heavy loadings. Organic P in solution in pig slurry can be expected, as was mentioned before, to remain completely mobile at pH values greater than 5. Indeed high concentrations of organic P in the effluent coincide with a pH value for the effluent well above 5. This influence of the pH probably also explains the 'double1 peak observed for organic P in the effluent of the soil column treated with freeze-dried slurry (Figure 3). Molecular weight characteristics of organic P in the column effluents were similar to those of organic P in pig slurry. Also (Table 7) the total amount of organic P eluted from the soil columns is roughly equal to that which can be expected from the amount of pig slurry or slurry solution brought into the column. In Figure 5 results are given of the analysis of the profile of the soil columns for organic and inorganic P. The distance over which inorganic and organic P have penetrated into the soil after 1 year under the conditions of the experiment is about 5 - 1 5 cm. An input-output balance of P and N in the soil columns was made and is given in Table 7. From the nitrogen data it follows that microbial action in the form of mineralisation and denitrification is well developed. The amount of organic N mineralised is considerably greater than the amount added, so the addition of slurry seems to have had a strong priming effect, particularly where slurry solution is added. This is not in agreement with practical experience where on average 70% of the organic N from manure is mineralised in the first year. According to Table 7, denitrification is high in both cases and relatively highest where slurry solution is added. Mineralisation of organic P appears to be less than can be expected from the experiment under static conditions. In the soil column treated with slurry solution even a net synthesis of organic P seems to occur. Apparently the N/P ratio is too high there. A high level of phosphatase activity in the effluents of the soil columns coincided with the peak of organic P. Apart from this peak in phosphatase activity, levels were almost zero, so that it is unlikely that micro-organisms are transported through the column. Calculating the pore widths
360-

through which water flow occurs at values of pF between 1 and 2 gives an indication of what size objects can migrate into the soil profile. For the sandy soil an upper (exclusion) limit of 10 to 100 ym was calculated, giving considerable obstruction to the movement of bacteria. Migration of viruses under these conditions is possible, as is indeed confirmed by the literature. Viruses appear to be mobile in the soil when the pH is above 7, whilst below 7 they become increasingly adsorbed. This phenomenon is somewhat analogous to the behaviour of organic P dissolved in pig slurry in the soil.
TABLE 7 INPUT-OUTPUT BALANCE FOR PHOSPHORUS AND NITROGEN IN THE SOIL COLUMNS TREATED WITH PIG SLURRY OR SLURRY CENTRIFUGATE AND PERCOLATED WITH WATER AT A RATE OF 1 cm/DAY. THE COLUMNS WERE ANALYSED AFTER 1 YEAR. P. inorganic (mg) Total content in: soil column + dried pig slurry soil column + slurry centrifugate soil column initial situation Cumulative content in the effluent of: soil column + dried pig slurry soil column + slurry centrifugate Content of: added pig slurry added slurry centri fugate Balance of: soil column + dried pig slurry soil column + slurry centrifugate P N organic (mg) N N 4 (mg)

organic (mg)

NO (mg)

2670 15 35 1450

1215 1045 1010

7220 6600 84 30

42 31 53

91 10 8

1.4 8.6 1180 170

10.3 31.9 250 20

520 670 1690 350

1180 1620 0 0

1900 3550 1420 4 320

+40 -76

-35 +47

-2380 -1510

+1170 +1600

+560 -770

361

COMPUTER SIMULATION OF P MOBILITY A computer simulation model was developed following a simplified and slightly modified version of the model used by Beek (19 79). The 'heart' of the model is formed by the adsorption isotherm for orthophosphate, measured after 24 hours under well-defined conditions (mainly pH, ionic composition of the soil solution). The phosphate adsorbed after 24 hours is considered to be easily exchangeable and thus mobile. After 24 hours phosphate is immobilised slowly according to a first order rate equation. Examples of this first order increase in immobile phosphate are shown in Figure 6 for a sandy soil. The results were obtained by incubating 250 g of soil in 500 ml solution in flasks mounted in an overhead shaker. From the plots an average half-life time for the soil reaction of phosphate of 35 days can be calculated. Results from applying the computer simulation model to 2 cases of soil columns treated with pig slurry are shown in Figures 7 and 8. In the added slurry only inorganic P was considered and modelled as ortho-P. As can be seen from Figures 7 and 8, prediction of phosphorus mobility with the aid of the computer simulation model appears to overestimate somewhat phosphorus mobility. This may be due to various slurry matrix effects on pH, Eh, competitive adsorption, adsorption kinetics etc. in the soil which are difficult to accommodate in a practical simulation model. It may also be concluded from a comparison of the areas under the profile distributions in Figures 7 and 8 that most of the organic P added with the pig slurry must have been converted to inorganic P, the difference in area between the profile distribution of the practical situation and the computer situation being roughly equal to the organic P added with the pig slurry. Work in this area is still in progress and results should be published soon (De Willigen et al.).

362-

In ( PM - P M E )

70 80 time(days)
F i g . 6: P l o t s of t h e l o g a r i t h m of mobile phosphate as a function of t i m e . 250 g o f a s a n d y s o i l was s h a k e n w i t h 500 ml s o l u t i o n c o n t a i n i n g : 50 ppm o r t h o - P , o 0 ppm o r t h o - P , 5 ppm o r t h o - P , V 0 ppm o r t h o - P , 0 . 0 0 5 N Ca+Na+K c h l o r i d e s ( 3 : 1 : 1 ) O.0O5 N Ca+Na+K c h l o r i d e s ( 3 : 1 : 1 ) 0 . 0 0 0 5 N Ca+Na+K c h l o r i d e s ( 3 : 1 : 1 ) 0 . 0 0 0 5 N Ca+Na+K c h l o r i d e s ( 3 : 1 : 1 )

PM i s t o t a l m o b i l e p h o s p h a t e and PME i s t h e e q u i l i b r i u m v a l u e a t i n f i n i t e t i m e , b o t h i n mg P / c m 3 s o i l . PME was e s t i m a t e d by t r i a l a n d e r r o r a t 22 mg P / c m 3

363-

500

1000/J g

P/g game

P AP

t l ' morgan

35 cm depth

Fig. 7.

Profile distribution of the increase in inorganic P in the soil profile after adding 80 g (A) and 2 0 g (B) of lyophilized pig slurry through the top 2 cm of a sandy soil column and simulating a rainfall of 2 150 mm in 16 months (A) or 3 60o ram in 12 months (B). The dried slurry contained 16.4 m g inorganic-P and 3.7 m g organic P/g. The doses are equivalent to about 1 OOO t/ha (A) or 250 t/ha (B) of pig slurry with a dry matter content of 7%. Drawn lines are actual situations, dashed lines were calculated by computer for similar conditions, considering inorganic-P only and assuming it to behave as orthophosphate. Unsaturated flow conditions were m a i n tained in the columns. Evaporation from the soil column surface was negligible.

364-

) c

500
I jl i
i I 1 I i i

OOOyu 100C
i

g P/g

A 'morgan game

5
"i

10

1 I

15 "
i I

20 "

25

J _ _ _ _ _ _ _ _

30

?5

cm depth

Fig. 8.

Profile distribution of the increase in inorganic P in the soil profile after adding 80 g lyophilized pig slurry through the top 10 cm of a sandy soil column and simulating a rainfall of 3 600 mm in 12 months. The drawn line represents the actual situation after 12 months. The dashed line represents the computer calculated situation for similar conditions and considering only added inorganic phosphorus. Experimental conditions are similar to those in Figure 7. The dried slurry contained 15.3 mg inorganic P and 3.2 mg organic P/g.

-365-

REFERENCES Ahmed, B. Beek, J. 1976. 1979. Mineralisation of inositol hexaphosphate in soil at varying Plant and Soil 44, 253-256. Phosphate retention by soil in relation to waste disposal. 1977. Simulation of Phosphorus static moisture levels.

Thesis Agricultural College, Wageningen, The Netherlands. Cole, C.V., Innis, G.S. and Stewart, J.W.B. Cycling in Semi-arid Grasslands. Fukurawa, S. 1968. Ecology 58_, 1-15.

Contribution of organic phosphorus to the increase of Abstract in Soil Science and Plant Nutrition 15(1969) Phosphorus compounds in pig slurry and their retention In: Utilization of manure by land spreading. 5672e. 257-277. 19 78. Dissolved organic and inorganic CEC

easily soluble P in waterlogged soil, especially related to phytic phosphorus. 243. Gerritse, R.G. 1979. in the soil.

publication EUR

Gerritse, R.G. and Eksteen, R.

phosphorus compounds in pig slurry. J. Ag. Sci. (Cambridge) 90_, 39-45. Gerritse, R.G. and Zugec, I. 1977. The phosphorus cycle in pig slurry 32 measured from PO distribution rates. J. Ag. Sci. (Cambridge) 8_, 101-109. Gerritse, R.G. and van Dijk, H. Gerritse, R.G. H.P.L.C. 1978. 1978. Determination of phosphates activities of soils and animal wastes. Soil Biol, and Biochem. 10, 545-551.

Assessment of a procedure for fractionating organic

phosphates in soil and organic materials using gel filtration and J. Sci. Food and Ag. 29_, 577-586. 19 77. Amounts and Mineralization of organic Islam, A. and Mandal, R. Bangladesh.

phosphorus compounds and derivatives in some surface soils of Geoderma 17, 57-68. In preparation. Computer de Willigen, P., Raats, P.A.C. and Gerritse, R.G. simulation of phosphate mobility in soils.

366-

DISCUSSION
H. Tunney (Ireland)

When you are talking about organic phosphorus, do you in clude biomass phosphorus, that is phosphorus in bacterial cells as organic phosphorus?
R. Gerritse (Netherlands)

This is important; it depends on the way in which you analyse the phosphorus. If you have a very subtle extraction method and a very subtle analytical method to determine the phosphorus, then you can assume that the phosphorus that you are extracting and determining represents the actual situation in the soil. But, in general, methods are fairly aggressive so you can assume that the rather labile organic phosphorus such as might also be contained in microorganisms, is decomposed and is partly determined as inorganic phosphorus. We have used several methods in doing this. We have done an extraction using TCA in which the bulk of the inorganic phosphorus and some of the organic phosphorus is extracted. The organic phosphorus extracted with TCA is not decomposed by enzymatic effects because the TCA de natures enzymes in solution. So, it sort of stabilises from a biochemical point of view, but the organic phosphorus in solution remains as such at least, that is what you hope. After that the remaining soil was extracted with sodium hydroxide containing EDTA. The EDTA masks the various trace elements which are necessary for enzymatic action. So, again in this case, you get a biochemical fixation. If you do repetitive extraction, first using TCA, and then extracting the remaining soil of slurry with sodium hydroxide EDTA, then the solutions you obtaiir can be analysed for total phosphorus "and for inorganic phosphorus but it is fairly difficult. The inorganic phosphorus can be deter mined directly using, for instance, Murphy and Riley but then you add sulphuric acid, creating aggressive circumstances which might affect the organic/inorganic phosphorus ratio in the extracted solution. With phosphorus, it is very difficult to get exactly the compounds you want.
367-

H. Tunney In your pig slurry samples was all the organic phosphorus soluble? R. Gerritse No, 1% of total phosphorus was in solution in the form of organic phosphorus, amounting to about 20 mg/1 P. This phosphorus was mainly high molecular weight, DNA related. But it is only about 1% of total P and roughly 10 or 20% of total organic P. The organic phosphorus is roughly 20% of total P and of this 20% roughly 5 to 10% is organic phosphorus in solution.
O.J. Furrer (Switzerland)

I wonder whether the soluble organic P fraction can be decomposed by micro-organisms? R. Gerritse This is true because the results I have shown were concerned with soil columns to which very high amounts of pig slurry had been applied, up to 1 000 t/ha. Going down to 100 t/ha it was very difficult to see the organic phosphorus eluting from these columns mainly because the background level of organic phosphorus in the effluent from the soil columns was such that the increase due to the pig slurry was almost negligible. I think that up to about 500 t/ha you will see very little effect of organic phosphorus in solution. However, increasing this up to 1 000 t/ha, or even higher, and especially with the high infiltration rates that we used, then you will elute all the organic phosphorus because maybe the micro-organisms have not had time to attack them. A. Cottenie (Belgium) Copper is one of the elements which is very easily incorporated in organo/mineral complexes but I think this might not be extended to an element like zinc where the stability constants for the formation of complexes are much lower than for copper.

368-

H. Kick (FRG) Can the dissolved fraction in the solution be absorbed by the roots? R. Gerritse I wouldn't know; it would be interesting to study this. It could be although I think the literature states that phosphorus is mainly dissolved in the form of orthophosphate. H. Kick But this compound is in a form that can be absorbed by the roots. It this a true solution or only a colloidal solution? R. Gerritse We centrifuged at 40 000 g and then we performed gel permeation. Thus we take it to be a true solution.

369-

THE EFFECT OF VERY INTENSIVE DRESSINGS OF LIVESTOCK EFFLUENT ON PHOSPHORUS IN SOIL J.P. Destain Station de Chimie et de Physique agricoles, Centre de Recherche Agronomiques, 5800 Gembloux, Belgium. ABSTRACT The phosphorus heavy dressings of in soil slurry. that in the deep loamy soil at Gembloux, nearest slurry the was studied in an experiment using very

It was established led to an increase surface.

in all forms of P, but only in the layer

The amount of exchangeable determine the enrichment in livestock (P contained effluent

P was not sufficient Since being technique partly organic),

to allow

us to gradually

of the soil-

it only increased

the use of the proposed.

Chang and Jackson

fractionation

was therefore

371

INTRODUCTION The concentration and size of livestock herds very often prevent full agronomic use being made of the effluents that are produced. The quantities are often excessive if they are to be applied in a given spot, and in view of the high cost of transport the only solution is to sacrifice a plot of land for use as a stockpile. Besides weighing up the agronomic risks that this practice involves (the chances of the plot being used again for growing crops), it seemed to us that it would be interesting to measure its impact on the environment (accumulation in the soil, percolation and the possibility of the nutritive elements being drawn down towards the water-bearing strata). In this paper we will consider in particular the problem of the phosphorus in the soil. 1. SYNOPSIS OF THE EXPERIMENT In one of our test fields at Gembloux, on deep loamy soil that is slightly polluted with foul matter, six plots of land measuring 8.3 m by 4.2 m were used for the experiment. Between 19 76 and 19 79, 4 dressings of cattle and pig slurry or fertilisers added to water were applied, as shown in Table 1. To prevent the effluent from running off to either side, small dykes were erected on the boundary of the plots which are never worked and which are over-run by vegetation that varies from one dressing to the next. Average composition of the slurry Cattle slurry: Pig slurry N 1/QO, ?205 L 4 2 / 0 0 ' K 2 5 - 8 7 % o ' MgO 0.71/ of fresh matter; ^ 'oo N 7.40 o / OQ , P 2 0 5 5.61/ QO , K 2 0 4.60/Oo, MgO 1.66/ of fresh matter, oo
- 372-

With particular regard to the phosphorus, the total deposits expressed in kg of P2C>5/ha represent approximately: Plot: LI 1 500 kg in slurry form dressed in 4 applications L2 3 000 kg in slurry form dressed in 4 applications L3 4 410 kg in slurry form dressed in 4 applications L4 3 780 kg in mineral form (super-phosphate) dressed in 3 applications L5 5 910 kg in slurry form dressed in 4 applications L6 1 500 kg in slurry form dressed in 2 applications.
TABLE 1 SYNOPSIS OF THE EXPERIMENT Date of appl ication Treatments 29/7/76 Quantity* 1 2 3 4 5 6 171 CS 300 CS 450 CS 402 water 6CO CS 363 CS 20/4/77 Quantity* 150 CS 371 CS 450 CS 400 water+F 600 CS 26/6/78 Quantity* 192 PS 278 PS 428 PS 400 water+F 534 PS 298 PS 3/8/79 Quantity* 197 CS 290 CS 429 CS 4O0 water+F 543 CS

Thousands of litres/ha CS: Cattle slurry PS: Pig slurry

F: F e r t i l i s e r s p l u s a m e l i o r a t o r s r e p r e s e n t i n g t h e t o t a l q u a n t i t y d e p o s i t e d by t r e a t m e n t 3. 2. SOIL SAMPLING AND ANALYSES

Up t o November 1979, 8 s o i l samples were taken a t depth (1.05 m) and subjected to the various q u a n t i t a t i v e a n a l y s e s . Furthermore, i n d i v i d u a l analyses for phosphorus are e i t h e r in hand or have already been completed.
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3. DETERMINATION OF THE EXCHANGEABLE PHOSPHORUS Extraction is according to the AL method (Egner et al., 1979). The figures from the analyses of 8 samples in 4 typical plots (Numbers 1, 3, 4 and 5) are set out in Table 2. We have not taken into account the soil below 60 cm because the P content measured there was too low. As the dressings of slurry progressed, a constant and marked increase in the amount of exchangeable P in the soils was recorded, mainly in the top layer (0 - 15 cm) but also to a lesser extent in the second layer (15 - 30 cm). In plot 4 (L4), the first application of fertilisers (superphosphate) led to a substantial increase in the exchangeable stock (SS 21), but there was no evidence of migration towards the lower layers. This phenomenon was repeated for the 2nd and 3rd applications of mineral P (SS 31 and SS 41) but, as distinct from the slurry plots, there was a tendency for the P content to decrease between dressings (SS 22 and SS 32) . In fact, mineral P deposited by the fertilisers is completely soluble (super-phosphate) and acts directly and without delay on the exchangeable stock in the soil; subsequently, it undergoes the process of retrogradation (influence of the Ca, Al and Fe ions in the soil). Moreover, quite a lot of the P contained in the slurry is present in organic form and must undergo mineralisation before it can increase the exchangeable reserves. Hence retrogradation does not occur until later. For this reason, we thought that it would be interesting to establish the different forms of P present in some of our samples using Chang and Jackson's fractionation technique.

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TABLE 2 EXCHANGEABLE P (AL) IN mg/100 g OF SOIL* Date of application Depth SS 0 7/76 0 15 30 45 0 15 30 45 0 15 30 45 0 15 30 45 SS II 9/76 28.0 26.2 16.7 5.41 29.4 29.2 12.4 7.18 26.3 26.2 18.8 10.4 32.4 30.5 . 16.7 6.81 SS 12 3/77 27.9 24.7 11.2 6.22 34.5 28.6 4.93 4.97 29.1 30.4 9.22 4.06 35.9 27.3 5.52 5.50 SS 21 7/77 34.7 27.7 12.0 4.68 36.7 28.2 8.66 8.28 62.2 32.5 12.3 5.29 41.9 29.3 9.43 3.68 SS 22 4/78 34.8 27.2 17.7 7.29 47.6 41.8 14.8 13.5 40.2 29.7 13.4 6.76 47.6 32.7 10.2 6.64 SS 31 9/78 23.4 29.9 2.58 14.4 33.4 32.3 28.2 10.6 71.2 35.5 12.8 12.1 37.6 25.7 8.50 12.10 SS 32 8/79 32.4 15.6 4.90 2.60 40.1 17.9 3.80 3.00 54.6 17.8 8.10 2.00 62.2 33.6 8.80 1.80 SS 41 11/79 80.4 31.8 4.80 3.20 72.0 31.4 16.2 3.00 112 37.4 5.80 2.20 167 45.4 8.40 1.80

LI

_ _ _ _ ~

15 30 45 60 15 30 45 60 15 30 45 60 15 30 45 60

cm cm cm cm cm cm cm cm cm cm cm cm cm cm cm cm

26.2 28.5 7.65 4.89 29.7 27.2 6.98 3.82 27.9 27.5 4.89 3.59 27.3 26.2 5.73 4.92

L3

L4

L5

The first digit of the sampling figure indicates after which application it was carried out; The second digit indicates whether it is the first or the second sampling after the application e.g. SS 21 = first sampling after the 2nd application SS 22 = second sampling after the 2nd application.

4. FRACTIONATION OF P ACCORDING TO C HANG AND JAC KSON The preceding method (AL) does not enable us to determine the chemical state of the P in our soils; the extracted quantities in fact comprise various phosphated constituents which are present in differing amounts. In contrast, Chang and Jackson's method makes it possible to extract the following 4 fractions by means of an appropriate reagent successively: 1) Fraction 0 made up of the exchangeable P and readily soluble; 2) 3) 4) Fraction A made up of aluminic P; Fraction B made up of ferric P; Fraction C made up of calcic P.

Table 3 shows the results of the analysis at the start of the experiment and the outcome after the final sampling of plots 3, 4 and 5 in November 1979, in which only the first two layers (0 - 15 and 15 - 30 cm) were considered. The soil has clearly been enriched by fraction 0, but only in the first layer 0 - 15 cm deep. The picture is the same for the other three fractions, with a fair degree of surface enrichment and hardly any difference - except in the case of fraction B - between the mineral phosphate (L4) and the phosphorus deposited by the slurry. In order to discover the amount of organic phosphorus, we also established the total P content of the plots (Table 4 ) . Once more it is evident that the P in these three soils has not migrated.

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TABLE 3 FRACTIONATION OF P ACCORDING TO CHANG AND JACKSON (IN mg/lOO g OF SOIL)

Depth:

O - 15 cm Before 1st application

November 1979 L3 29.00 23.50 23.75 26.00 102.25 L4 30.75 25.50 16.25 66.OO 138.50 L5 52.00 17.50 25.OO 66.50 161.OO

Fraction 0 Fraction A Fraction B Fraction C Total mineral

7.50 7.00 11.25 18.50 44.25

Depth: 15 - 30 cm

Fraction 0 Fraction A Fraction B Fraction C Total mineral

8.CO 6.50 6.25 31.50 52.25

6.50 6.50 15.OO 16.50 44.50

13.OO 11.0 11.75 30.00 65.75

TABLE 4 TOTAL P - HC1 O. METHOD (IN mg/lOO g OF SOIL) Novembe r 1979 LS 156.00 84.10 L4 164.00 90.40 L5 304.OO 94.10

Depth

Before 1st application 76.OO 77.70

0 - 15 cm 15 - 30 cm

The level of organic P is calculated by subtracting the amount of mineral P (the sum of the 0, A, B and C fractions) from the total P content (Table 5 ) .

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TABLE 5 ORGANIC P (IN mg/100 g OF SOIL)

Depth

Before 1st application 31.75 25.45

November 1979 L3 53.75 39.60 L4 25.50 L5 143.00 28.35

O - 15 cm 15 - 30 cm

As would be expected, there is considerable accumulation of organic P in the surface layer of the plots of land dressed with slurry. 5. CONCLUSIONS The considerable quantities of P deposited by very heavy dressings of slurry lead, in our soils, to increases in the P content solely in the layers nearest the surface. This may be partly accounted for by the phenomena r>f fixation and retrogradation. Furthermore, the P contained in livestock effluent is partly organic and as a result there is only a gradual increase in the amount of exchangeable P in the soils.

REFERENCES

Chang, S.C . and Jackson, M . L . , 1 9 5 7 . Soil S c i . 83_, 113-144.

Fractionation of soil phosphorus.

Egner, H., Riehm, H. and D o m i n g o , W.R., 1969.

C hemische ExtraktionsK. Lantbrukshflghsk.

methoden zur Phosphor- und Kaliumbestimmung. Ann. 2 6 , 199-215.

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APPENDIX

Exchangeable P (AL. Method) 0-15 cm

4410 SF 3780 MF 5910 SF

I I 7/76 lr , 3/77 , 9/76 7/77 S ' S1 F

4/78 S'F

, 9/78

++ 8/79 11 S'F

Sampling date

379

APPENDIX 2

Exchangeable P (AL Method) 15-30cm

O

(/)
O)

o o

0>

6050'

UIOSF 3780MF 5910 SF

Tr3 Tr4 Tr 5

4 CM 30
2010-

0'

7/76

3/77 7/77 S'F

A/78

9/76

9/78

8/79

11/79

Sampling dale

s1

S'F

380-

APPENDIX 3

300-

Fractionation of Soil - P (Chang and Jackson M.)

O)

82501

E 200-

0-15 cm

150 5.0rg.P A.C(PCa) 100Total P< 3B(PFe) 2.AIPAL) 503 1 St 76 L3 Nov 79 LA Nov 79 L5 Nov 79 LOlExchP]

o10O
in oi

15-30 cm
5

o o
**

Q_

b0E

0-

1
st 76 L3 Nov 79 LA Nov 79 L5 Nov 79

-381

PROBLEMS RELATED TO PHOSPHORUS IN THE DISPOSAL OF SLURRY J.S.V. McAllister and R.J. Stevens Department of Agriculture, Agricultural and Food Chemistry, Research Division, Newforge Lane, Belfast, BT9 5PX, UK. ABSTRACT Data are presented result excreta nutrient in excessive levels by under intensive while showing how heavy applications of phosphorus systems Experimental the greatest P levels. is from point in soil. grazing at present of slurry The return of can of in soil drainage of that slurry.

accumulation in paddocks. agriculture in increased

can produce wide variations studies risk sources, Lysimeter as great and surveys of phosphorus the application studies as that suggest from

water show that contamination slurry enrichment

does result

from farmyard

manure is at least

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INTRODUCTION In Northern Ireland the climate is cool and humid. Consequently the amount of arable farming is restricted and at present over 90% of the farm land is under grass. and in intensive units. Topography in Northern Ireland is also difficult from that in the rest of the United Kingdom in that much of the drainage flows into large, relatively shallow lakes. water. This increases awareness of the phosphorus content of drainage While the use of fertilisers in Northern Ireland is somewhat lower than in other areas of the United Kingdom it should be remembered that: (a) the proportion of land under arable crops is low, and (b) the intensity of livestock production is high with large quantities of feedingstuffs being imported. The increase in fertiliser and manure dressings has been reflected in the results of analyses on advisory soil samples. In the mid-1960's concern was also arising over possible effects on the N and P contents of drainage water. A nutrient balance for agriculture in the province in 1965 prepared from calculated imports and exports of the major nutrients (McAllister, 1971) showed an excess of 20 kg P and 25 kg K/ha/year. With such average values it was obvious that the more intensive farms would have considerably higher excesses. Indeed a similar calculation for such a farm showed excess inputs of 149 kg P and 203 kg K/ha/year. Subsequent work by Adams and McAllister, 1975 has shown the effect of excreta from pigs and poultry in producing such surpluses. Present day agriculture is essentially livestock production on grassland

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The major disadvantages relating to phosphorus from the frequent application of slurry are: (a) excessive accumulation in soil (b) enrichment of drainage water EXCESSIVE ACCUMULATION IN SOIL It is now well known that frequent heavy dressings of slurry will produce a build-up of soil nutrient levels. Table 1 (McAllister, 1973) gives analyses for soils from adjacent pasture plots, one untreated and the other manured with an average 3 dressing of 212 m /ha pig slurry per year for 8 years. There has been a marked accumulation of phosphorus and potassium and a build-up of organic matter in the top 15 cm of the treated soil. There appeared to be little movement of phosphorus below is not always so (McAllister, 1971; O'Callaghan 30 cm but this

and Pollock, 1976).

TABLE 1 CHEMICAL PROPERTIES OF A GRASSLAND SOIL PIG SLURRY FOR 8 YEARS) (A - UNTREATED; B - 212 m /ha/year

Extractable* (mg/kg air dry soil) Soil depth Carbon Nitrogen

( % )
A B 5.1 2.2 0.9 0.5 0.4 A

( % )
B 0.71 0.25 0.11 0.04 0.03 A 15 2 1 1 2

P B 154 15 2 1 1 A 135 50 37 39 41

K B 570 115 60 62 79 A 16 11 5 4 3

Cu B 38 15 8 5 4

0-15 15-30 30-45 45-60 60-75

4.5 2.0 0.8 0.4 0.3

0.58 0.21 0.07 0.03 0.02

Nutrients extracted by N ammonium acetate/acetic acid solution at pH 4.2.

385-

Recently analysis of a permanent pasture (Table 2) which had received very heavy dressings of pig slurry for at least 15 years showed a total P content in the top 7.5 cm of 0.6 6% and very high levels of extractable P to at least 45 cm depth. The prospects of recycling such accumulations are poor.
TABLE 2 ANALYSES OF UNDISTURBED PASTURE SOIL HEAVILY DRESSED WITH PIG SLURRY Air dry soil % P (total) 0.87 0.46 0.22 0.09 0.05 mg/kg P (extractable) 642 371 225 61 17

Soil layer | (cm)

1

0 -

lh

, 7h - 15
15 - 30 30-45 1 45 - 60

The uneven application of slurry and more especially the return of excreta by animals under intensive grazing systems can result in wide variations in soil nutrient levels. Analyses for individual soil cores from two grazed paddocks are shown in Table 3. Such variations would cause problems in soil sampling and analysis and could have adverse effects on plant growth. ENRICHMENT OF DRAINAGE WATER Marked phosphorus enrichment of drainage water by agricultural activities appears to arise mainly by direct contamination from point sources. Table 4 compares the nutrient content of drainage water from four grassland farms of different stocking densities in the same catchment area (Gibson and Smith, 1973) and shows that the loss of inorganic N, mainly nitrate-N, increases with the intensity of farming. The phosphorus content of the drainage water is markedly lower from the hill farm but remains independent of the stocking rate on the lowland farms.
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TABLE 3 COMPARISON OF ANALYSES OF 50 INDIVIDUAL SOIL CORES (0 PADDOCKS 10 cm) FROM TWO

mg/kg air dried soil Paddock Variable Mean I P K 1 Na Mg Ca P K 2 Na Mg Ca 30 246 82 833 7 080 28 386 1O0 815 6 344 7.5 174.5 19.9 121.4 578.1 11.2 297.0 25.8 141.2 528.7 Std. Dev. Minimum 18 81 42 638 5 810 14 81 47 637 5 220 Range r Maximum 49 846 128 1 113 8 290 62 995 174 1 228 7 270

TABLE 4 EFFECTS OF STOCKING DENSITY ON THE NITRATE AND ORTHOPHOSPHATE CONCENTRATIONS OF DRAINAGE WATERS Source of land drainage Soluble orthophosphate (mg P/1) 0.020 0.044 0.048 0.042 Inorganic nitrogen (mg N/1) 1.02 5.47 6.18 6.68

Hill farm (less than 0.62 DCE/ha) Farm 1 (0.86 DCE/ha) Farm 2 (1.66 DCE/ha) Farm 3 (3.98 DCE/ha)

DCE = dairy cow equivalent.

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A recent survey of 17 streams from known catchment areas (McAllister et al., 1976) also suggested that stocking intensity had little direct influence on phosphorus concentration. In this survey, the few cases of increased phosphorus levels were associated with contamination by yard or road drainage. Nevertheless it has been found (McAllister, 1976) as shown by the data in Table 5 that when slurry is spread under suitable conditions eg. when the soils are waterlogged the phosphorus content of the drainage water is increased. Possible mechanisms for this are discussed later.
TABLE 5 COMPOSITION OF DRAINAGE WATER FROM SITES A AND B BEFORE AND AFTER THE APPLICATION OF SLURRY Hours after spreading Flow rate (1/hour) A 955 964 976 970 942 888 1 042 1 042 B 1 022 1 076 1 106 1 031 1 104 570 783 4 200 A 3 10 5 3 2 2 neg. neg. BOD (mg/1) B 4 53C 215 34 7 7 3 3 COD (mg/1) A 14 21 15 18 18 14 16 12 B 128 947 427 179 90 46 27 69 N (mg/1) A 18 18 19 17 8 10 10 7 B 6 91 36 12 6 7 5 5 P (mg/1) A 0.06 0.28 0.20 0.13 0.07 0.06 0.05 0.04 B 1.27 9.54 3.69 1.17 0.37 0.45 0.16 0.65

nil 0.5 1 2 4 8 24 48

A more detailed study on one field drain has been carried out. The catchment area of the drain was 5 hectares of gently sloping medium heavy loam under intensively farmed grassland. The drain was monitored from November, 1976 to March, 1978. Fertiliser usage during the study was about 250 kg N/ha/year; phosphorus and potassium being applied mostly as slurry. Flow rate in the drain was measured continuously and sub-samples were taken every half hour by automatic liquid samplers and subsequently combined depending on flow rate fluctuations.
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Nine hundred and thirty samples were obtained for analysis during the 405 days when both flow recorder and sampler worked satisfactorily. The samples were analysed for total-N, nitrate-N and three forms of phosphorus, total-P, ortho-P and soluble reactive-P. The high rates of nitrate-N loss occur during the October to March period which carries 90% of the annual flow. Discharge is almost negligible from June to September. The average 12 month loss rate was 34 kg N0,-N/ha/ year but because of the dependence of flow upon rainfall and evaporation an accurate nutrient loss study would require monitoring over several years. Phosphorus loss rates were much less predictable than nitrate loss rates and were influenced by factors other than rainfall. The relationship between soluble reactive phosphorus.concentrations and flow rates is shown in Figure 1. IiT'the majority of observations concentrations were less than 200 yg P/l. The soluble reactive phosphorus concentration in land drainage water resulting from soil mineral phosphate dissolution would be expected to be less than this value. The high concentration points would be grouped and assigned to specific events, namely the application of slurry. Slurry application was found to cause contamination of the drainage water both in low flow conditions as in March 1977 and when there were high flow conditions immediately subsequent to slurry application as in February 1978. The average annual loss of soluble reactive phosphorus from the land drain was 0.22 kg P/ha/year. This amount of phosphorus loss is not agronomically important but it could be important environmentally, particularly when the drainage water is eventually impounded in a lake or reservoir. The effect of the direct contamination by the slurry application in March 1977 accounted for about 1% of the annual load. The soluble reactive phosphorus loss in the high flow conditions after slurry application in February 1978 accounted for 35% of the annual load. The losses of slurry nutrients may be due to the flow of liquid in continuous microporous channels within the
- 389-

1000 *
s

/ /
S

800 -

'* Slurry application 7-3-77 / /

* . /

/ / / Slurry application 22-2-78

E
a. u c o u K
C/3

600

: 400 ;

,
1

: i

200

- : - "

t > y * t t > ^ t

mm > n>

^t* ,

0
Fig. 1.

5 6 Flow - rate I. sec"

1 0

Soluble reactive phosphorus V. flowrate for land drain.

soil structure and there may be two possible effects from slurry applications. Firstly there may be a direct immediate contamination of the drainage water, a contamination greatly enhanced by high flows immediately subsequent to slurry application. Secondly slurry phosphorus may remain in solution in the soil pores for long periods before it is metabolised into the soil organic matter and soil mineral phases. During this period of long term contamination high flow conditions may again result in drainage water with enhanced phosphorus concentrations. Kolenbrander (1973) has also drawn attention to the problem of phosphorus leaching and to possible harmful effects from quite small increases. LYSIMETER STUDIES The effects of manuring on the mineral composition of drainage water have been studied using 24 small lysimeters. There were 3 sets of 8 lysimeters, each set containing soil derived from a different parent material - Silurian, Bunter Sandstone and basaltic till. In each set, 4 lysimeters were sown to grass and the other 4 kept fallow and free from weeds. The lysimeters were filled and the grass sown in summer 19 68. The manurial treatments applied to each sub-group of 4 have been nil, NPK fertilisers, slurry and farmyard manure. The soils in the lysimeters took almost three years to settle fully and other results from 1971 to 1977 have been used in calculating the quantities of nutrients in the leachates presented in Table 6. During the experimental period 3 dressings each equivalent to 91 kg N/ha were applied each year by all the manurial treatments. The phosphorus and potassium contents of the fertiliser treatments were adjusted to be equivalent to those of the slurry treatments. These supplied average dressings of 95 kg P and 110 kg K/ha/year. Such adjustment was not possible with the FYM treatment which supplied 57 and 72% more P and K respectively than the other manurial treatments.

391-

TABLE 6 NUTRIENTS IN LEACHATES FROM LYSIMETERS (1970-77) F allow surface Soil parent material No manure NPK fert. Slurry FYM No manure Grassed surface NPK fert. Slurry FYM

N0 3 -N (kg/ha/year Silurian Basalt Bunter Sandstone 144 76 197 355 267 305 285 158 251 131 64 189 6.2 2.1 2.2 13.1 3.1 0.7 5.0 3.0 1.1 12.1 1.6 1.5

P (g/ha/year) Silurian Basalt Bunter Sandstone 226 560 197 205 265 197 316 1009 303 880 2 295 248 466 244 466 380 363 124 611 312 162 1342 658 509

K (g/ha/year) Silurian Basalt Bunter Sandstone 120 2 21 283 2 76 231 1 66 73 2 52 16.5 3.6 2.0 61.8 0.9 1.0 21.2 0.6 1.1 41.2 0.8 2.2

The average volume of leachate from the lysimeters with bare surface was 131.5 1/year and neither treatment nor soil type had any effect on it. From lysimeters with grassed surface the mean volume of leachate was 82.6 1/year, approximately 63% of the volume when the surface was bare. The quantity of leachate under grass was consistently higher when no fertiliser or manure was applied presumably due to less vigorous grass growth resulting in less transpiration. The main effects of treatment may be summarised as follows: Nitrogen - the quantities of N0..-N leached were, as would be expected, much greater from the lysimeters with bare surface and while FYM had little effect on the amount leached both fertiliser and slurry increased it in proportion to the amounts of soluble-N they supplied. The amounts leached from the
392-

basaltic soil were considerably less than those from the other soils. Under grass the quantities leached were much smaller with the amounts from the Silurian soil being consistently greater than those from the other soils. Phosphorus - the average annual loss of total P was much less than that of NO-.-N; values in excess of 1 kg/ha/year were recorded for only 3 lysimeters. Losses from unmanured lysimeters were equal to or greater than those from the fertiliser treatment except for the basaltic soil under grass. Apart from the Bunter Sandstone soil with bare surface, P was most mobile in the FYM treated lysimeters irrespective of surface condition. Slurry treatments also generally gave values greater than either the fertiliser or control treatments. This again suggests some direct movement of P from organic manures into drainage water although even the highest levels recorded for slurry and FYM represent only 0.5% and 1.2% respectively of the P applied. All other values for slurry were under 0.1% and for FYM under 0.6%. Potassium - the greatest losses of K were from the Silurian soil under fallow. Losses were also relatively high from this soil under grass. The Bunter Sandstone soil also lost appreciable amounts of K under a bare surface but only small amounts under grass. Losses from the basaltic soil were small under both surfaces. The fertiliser treatment and to a lesser extent the 'slurry treatment increased losses of K under fallow on both Silurian and Sandstone soils. The results of both field and lysimeter studies therefore suggest that the application of organic manures may, under certain conditions and unlike mineral fertilisers, increase the phosphorus content of drainage water. PHOSPHORUS INPUT TO LOUGH NEAGH Lough Neagh is the largest inland lake in the British Isles and the Freshwater Biological Investigation Unit, DANI has carried out investigational work in the Lough since 1968.
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Much of the research effort has been concentrated on the nitrateN and soluble reactive P budgets. Loadings from the major rivers entering the Lough are available for the period 1971-78. The soluble reactive P load appears to have been relatively constant at 200 tonnes P/year but the annual nitrate-N load has increased from 3 803 tonnes to 6 159 tonnes over this period. In addition to quantifying the nutrient inputs it has also been important to identify their sources. This is particularly so for soluble reactive P, considered the limiting nutrient for algal growth in the Lough. Lowering the P input should lead to a reduction in algal biomass . The factors controlling the soluble reactive phosphorus loads in the major inflowing rivers were identified by a multiple step-wise regression analysis approach, correlating inputs expressed as a loss rate per hectare with catchment characteristics as independent variables (Smith, 1980). The variables included were sewered population, unsewered population, proportion of lowland (below 213 m) within the catchment area, annual flow, the log transformation of annual river flow, meat processing, milk processing, stocking density and excreta production (stocking density weighted for the time animals are kept indoors). The analysis showed that four factors, namely sewered population, log river flow, lowland area and milk processing, accounted for 80% of the total variation in phosphorus loss rates. The most important variable was sewered population, confirming the results of direct sewage treatment works surveys. The second most important variable was log river flow, suggesting that higher flows may lead to increased loss rates from land drainage. Differences in the proportion of land below 213 m were found to be significantly correlated, lowland having higher loss rates than hill land. Milk processing was just significantly correlated (P < 0.05). Meat processing, stocking

394-

density and excreta production were not significantly correlated with phosphorus loss rates. The regression equation was used to predict the amount of soluble reactive phosphorus entering Lough Neagh. Although there are direct measurements from the six major rivers covering 88% of the catchment area, the remaining direct drainage area accounts for 27% of the urban population. Using the average flow of the 1971 - 1978 period and 1978 data for population and milk processing, the predicted soluble reactive phosphorus load was 248 tonnes P/year. Of this 69% was contributed by sewage, 3% from milk processing and 38% from land drainage. Tertiary treatment of sewage effluents to remove phosphorus could be expected to reduce the phosphorus loading to the Lough by 50%. To achieve further reduction it would be necessary to restrict the contribution from land drainage, hence the importance of identifying the factors which can influence it.

395

REFERENCES Adams, S.N. a n d M c A l l i s t e r , J.S.V., 1975. Nutrient cycles involving Ireland. water.

p h o s p h o r u s and p o t a s s i u m on l i v e s t o c k J . A g r i c . S c i . Camb., 8 5 , P r o c . CICRA Symp. Kolenbrander, G.J., McAllister, J.S.V., 1973. 1971. 345-349. G i b s o n , C . E . and S m i t h , R.V. , 1 9 7 3 . Newcastle-upon-Tyne, 102-106. Fertilisers,

farms i n N o r t h e r n

A g r i c u l t u r e and t h e u s e of and t h e

Intensive agriculture

environment, quality. 1st

f a r m i n g p r a c t i c e and w a t e r

P r o c . F e r t i l . S o c . No. 1 3 5 , London. N u t r i e n t b a l a n c e on l i v e s t o c k f a r m s . P o t a s s i u m and s y s t e m s o f P r o c . CICRA Symp. Proc. Colloq. Potassium I n s t i t u t e Ltd. Farming, McAllister, McAllister, 113-121. 1973. 1976. Farm e f f l u e n t s . Intensive 71-79. related and J.S.V., J.S.V., Grassland

a g r i c u l t u r e and t h e e n v i r o n m e n t , N e w c a s t l e - u p o n - T y n e , t o the disposal of s l u r r y . water q u a l i t y , McAllister, J.S.V., Stevens, R.J.,

S t u d i e s i n N o r t h e r n I r e l a n d on p r o b l e m s

ADAS T e c h . B u l l . No. 3 2 , A g r i c u l t u r e A l e x a n d e r , G.C. and S u t t o n , G . K . , 1-7.

MAFF, 4 1 8 - 4 3 1 . 1977.

C h e m i c a l c o m p o s i t i o n o f s t r e a m w a t e r s i n C o u n t i e s A n t r i m and Armagh. R e c . A q r i c . R e s . , DANI, 2 5 , O'Callaghan, J.R. and P o l l o c k , K . A . , 1 9 7 6 . A land spreading t r i a l with pig

slurry.

ADAS Tech. Bull. No. 32, Agriculture and water quality, Private communication.

MAFF, 371-399. Smith, R.V., 1980.

396-

DISCUSSION R.E. White (UK) When you looked at the effect of flow rate on phosphate concentrations, was it a positive effect? In other words, did the concentration increase as the flow rate increased? Also, was this associated with an increase in particulate matter in the drainage? Does P concentration increase with flow rate? J.S.V. McAllister (UK) Under some circumstances there would be an increase in particulate matter but this was soluble reactive phosphorus. Phosphorus concentration increases with flow rate generally. T.W.G. Hucker (UK) You said that removal of sewage effluent was going to cause a problem. I realise it changes the emphasis but surely this is going to be a great help and it will lighten your load. J.S.V. McAllister I meant that it will present a problem to agriculturists. M. Webber (Canada) In Canada we are faced with the same situation, that having reduced the phosphorus from point sources then agriculture comes up looking not so good. We too are concerned with what to do. Does the manure that you are talking about have to be disposed in this particular catchment area and is the problem mainly manure as opposed to commercial fertiliser use, or some other source? J.5.V. McAllister There is no alternative to disposal in the catchment where we are using 75% of the total area. In the work we have done the amount coming through from fertilisers still seems negligible. The lysimeters did not show much. I would like to see all the
-397-

slurry solids incinerated converted to calcium phosphate and then applied that way. M. Webber Where you have applied manure, do you feel that the phosphorus you see moving through the soil is moving as a particulate material, associated with particulate? J.S.V. McAllister I think it is probably doing both. When we get that kind of flushing effect we think there must be some very small particles sitting in the channels and then being flushed out. If anyone has any theories as to why the farmyard manure is worse than the slurry I would be pleased to hear from them.

-398-

THE EVOLUTION OF PHOSPHORUS IN SEWAGE SLUDGE AFTER ITS APPLICATION TO THE SOIL G. Hanotiaux, J.P. Heck, M. Rocher, L. Barideau and 0. Marlier-Geets. Faculte des Sciences Agronomiques de l'Etat, Gembloux, Belgium. ABSTRACT The aim of the study soil of the different industrial relating and/or wastewater was to attempt combinations plants. to follow the evolution combinations matter. P. using that soil as total in urban observed Soluble

ahemioal

of P in sewage from

The chemical as well

were those

P to Al, to Fe, to Ca and to organic P have been characterised, 3 experimental the presence fields of total

and exchangeable After analyses it

studying

in which treatments it appears trace P can only

100, 300 and 450 m of sewage sludge to determine 37% of the amount added. is added. This raises element sludge at depth analysis. With regard differences between the control to the various and treated P therefore

were undertaken, disappears of verifying

a maximum of to which of this

from the soil the leaching

the question

or alternatively

of the unsuitability

of the method of

combinations plots

of P,

significant to Al fields. appeared

in soluble

P, exchangeable

P and P related in one of the 3

399-

INTRODUCTION The aim of this study was to attempt to follow the evolution of various fractions of P in sewage after its application to soil, particularly where it was possible that P might be leached at a certain depth. Indeed, although all research workers who have taken an interest in the P content of soil are unanimous in acknowledging the fixation of P arising from external sources (fertilisers) in the surface layers of agricultural soils, several have shown that P may leach as a result of complexation with certain natural chelatings existing mainly in the slurries where there is a possible risk of polluting the water tables (Vollenweider, 1968; Kolenbrander, 1972; Cooke, 1973 and Cottenie, 1972). By analogy it is possible to ask whether such a phenomenon is likely to occur in sewage. Initially, the study was undertaken as a trial using plots of land which were not especially intended for this purpose. These fields were chosen for 1) the study of the effects and after effects of sewage on the production of a crop of wheat and 2) the comparative study of the fertilising values of mineral nitrogen and sewage, and were situated at Beuzet and Fleurus respectively. The results from these fields enabled us to carry out a similar study on a plot trial, where it was possible to exercise a far more precise control over the different parameters taken into consideration in order to analyse P. These parameters were the analysis of each tank of sludge spread over the various plots and the determination of the apparent Specific Weight of the soil and subsoil of each plot. The latter field was set up at Gembloux. ANALYTICAL METHODOLOGY The same analytical techniques were applied as those described in the paper by Hanotiaux et al. (1980).

-400-

EXPERIMENTAL FIELDS 3 .1 Field at Beuzet This field was situated at Beuzet and is shown by the cartographical symbols Acp(c) and Ac/d a 1 (Avril, 19 78) . It comprised 3 blocks (3 repetitions), each made up of 5 plots (20 m x 12 m ) . It was sown with wheat which followed a maize crop. The plots chosen for the present study were the control 3 3 plots (0 m of sludge/ha) and those having received 100 m of sludge/ha. The sludge used came from Rhisnes. It was spread over the surface by means of a traditional muck-spreader. Table 1 shows the phosphate spectrum of the plots and the additional P_05 in kg/ha in 100 m of sludge containing 7.04% dry matter.
TABLE 1 PHOSPHATE SPECTRUM OF THE SLUDGE FROM RHISNES SPREAD AT BEUZET (RESULTS EXPRESSED IN mg P 0 /100 g DRY MATTER, IN % OF TOTAL P, AND IN Kg POr/ha) 2 5 v Fractions mg P 2 0 5 / lOO g D M % TP kg P 2 0 5 / h a 11.46 67 40.72 240 0.43 3 27.72 16 3 19.6 7 116 0 960 A 3 410 B 36 C 2 321 org. 1 647 total 8 374

loo
589

The addition of P in the treated plots was likely to cause an increase in the region of 8% in the total P content of the 0 to 0.15 m surface layer. The control plots received a mineral manure containing 100 kg of P-O^/ha. The soil was sampled at two levels, 0 to 0.25 m and 0.25 to 0.50 m, at the rate of 6 core samples per plot, taken
-401 -

with a mechanical borer. Sampling was carried out before the spreading of the sludge (Nov. 19 77) and after the harvest (Sept. 1978). The soil samples were analysed for the total P content and for the various fractions of P. DISCUSSION OF RESULTS There is no indication of significant differences in total P or the various fractions between the initial and final states in either of the 2 layers studied (Table 2 ) , either in the treatment of the control plot or in the treatment of the 3 100 m plots. On observation of the CV%, the absence of any significant difference becomes obvious, and has been confirmed by applying the Student 't' test of comparison of averages. Moreover, comparison of the standard - 100 m at the end of the cultivation season does not reveal any differences between the contents observed in both layers, whereas in the 100 m treatment, there is an additional 489 kg P-O^/ha from the sludge as compared to that present in the control plot (589 - 100 = 489 kg P ^ / h a ) . This observation raises the problem of the disparity of the added P, especially as there seems to be no enrichment of this element in the deepest horizon (0.25 to 0.50) . Field at Fleurus This field was situated at Fleurus. cartographical symbol Abao (Avril, 19 7 8) 3.2

It is shown by the

It consisted of 6 blocks (6 repetitions), each comprising 6 plots (15 m x 4 m ) . It was sown with winter wheat which followed a beetroot crop. The plots chosen for the study were in a field which was undergoing a special experiment designed to test the influence and cumulative effect of a nitrogen fertiliser and of an application of sewage.
402-

TABLE 2 FIELD AT BEUZET SOIL CONTENT OF TOTAL P AND OF VARIOUS FORMS OF P (RESULTS EXPRESSED IN rag P O / l O O g (AV) ACCOMPANIED BY THEIR CV%) Fractions
AV IS FS IS FS IS FS IS FS 0 CV% AV A CV% AV B CV% AV C CV% AV

Org.
CV%

P total
AV CV%

3.57 4.66 0.09 0.08 4.53 5.62 0.01 0.29

37.07 29.19 44.91 64.95 40.30 43.30

18.10 20.71 3.28 3.97 19.49 23.04 3.07 3.97

21.35 2.10 56.16 49.73 5.00 4.CO 34.80 40.49

37.85 40.90 17.71 16.77 38.10 38.54 15.26 11.17

22.49 17.37 38.59 30.5 7 5.80 9.00 20.OO 44.91

25.82 25.45 10.99 12.74 25.54 28.38 12.64 14.15

13.95 3.81 28.11 22.58 8.10 10.30 5 5 . 30 50.16

103.58 102.92 82.56 73.31 107.75 96.01 71.30 69.85

2.84 6.18 10.57 9.91 6.40 3.50 8.40 11.00

188.92 194.64 114.64 106.86 195.41 191.59 102.28 99.42

9.30 6.20 16.80 13.00 4.30 4.30 14.80 10.81

113.48

A V = a b s o l u t e value C V % = coefficient of v a r i a t i o n i n % sludge harvest IS = i n i t i a l s t a t e p r i o r t o c u l t i v a t i o n and s p r e a d i n g of FS = f i n a l s t a g e a f t e r

The sludge spread came from Fleurus. It was ploughed in by a muck spreader with injection system. It showed the phosphate spectrum described in Table 3, which also shows the presence of P25 ^n kg/ha in 450 m of sludge containing 5.60% dry matter. The addition of P in the treated plots was likely to cause an increase in the region of 18% in the total P content of the 0 to 0.25 m layer.
TABLE 3 PHOSPHATE SPECTRUM OF THE SEWAGE FROM FLEURUS SPREAD AT FLEURUS (RESULTS EXPRESSED IN mg P.0r/100 g DRY MATTER, IN % OF TOTAL P AND IN kg P Cl/ha) . 2 5 2 b Fractions mg P 2 0 5 / 100 g D M % TP kg P 2 0 5 / h a 0 1 030 A 2 855 43.04 719 B 142 2.14 36 C 1 658 24.99 418 org. 949 14.13 239 total 6 634 lOO 1 672

15.53 260

The soil from the control plots and the 450 m plots was sampled at three levels: 0 to 0.15 m, 0.15 to 0.25 m and 0.25 to 0.35 m. These fairly shallow levels were chosen within the framework of a study of the mobility of Zn added to soil by sludge. As a result of observations made on the field at Beuzet, which had proved difficult to interpret, the samples were analysed for forms of P and total P. Sampling was carried out by means of 25 core samples per plot taken with the use of a manual borer. This was carried out after the wheat harvest of 15/09/78. DISCUSSION OF RESULTS The results are shown in Table 4. They show the average values obtained from the 3 repetitions carried out at the end of the cultivation period.

TABLE 4 SOIL CONTENT OF TOTAL P AND OF THE VARIOUS FORMS OF P (RESULTS EXPRESSED IN mg P O/lOO g). Fractions Control 450 m3 Control 450 m3 Control 450 m
3

Org. 107.97 108.88 103.53 112.55 96.59 91.38

Total P 232.58 239.49 233.76 251.42 173.54 189.59

0-0.15 m

9.45 11.88 8.94 12.06 3.61 5.92

29.10 33.06 30.73 35.65 18.66 25.97*

35.98 39.61 42.86 42.63 29.99 35.09*

50.08 46.10 47.69 48.54 27.34 30.89

0.15-0.25m

0.25-0.35m

* test ' t' significant with a = 0.05 between control and 450 m" A test of comparison of averages 450 m (Student test 't') only

reveals significant differences between the control and the treatment for the fraction A and B in the deepest layer (0.25 to 0.35 m) , both for total P and for any of the fractions studied. A slight but significant increase is noticeable in the total P content depending on the depth. These increases in Allowing for the absolute value have been calculated and the total gain which they represent amounts to 6 31 kg P 2 0 g /ha. addition of P by the sludge (1672 kg P 2 0 5 / h a ) , there is a loss

of 1041 kg P 2 0 5 /ha in the first 35 cm depth of soil. 3.3 Field at Gembloux This field was situated at Gembloux and is represented by the cartographical symbols sEbx., g, sEbx 2 , (g)Lbpy (Avril, 1978). It consisted of 4 blocks (4 repetitions) each comprising 9 plots (15 m x 4.80 m ) . It was sown with maize.

-405-

The aim of the different treatments methods of applying sludge (spread on the in), following the evolution of organic N period of time and possibly measuring the on the soil structure.

was to compare the surface or ploughed in sludge over a effect of sludge

The treatments chosen for the study of P were as follows: - 300 m of sludge (exact quantity measured during spreading) - 0 m of sludge. The sludge spread came from Fleurus. In contrast to the previous field, the analyses were carried out on each tank of sludge spread in such a way as to measure as precisely as possible the addition of P on each plot. The sludge was ploughed in to a depth of about 0.10 m by a muck spreader with an injection system. Table 5 shows the average phosphate spectrum, as calculated for the 14 tanks analysed, and the average amounts of P in the various fractions for the 300 m J spread. The addition of total P was likely to cause an increase in the region of 21% in the degree of total P for the layer 0 to 0.25m.
TABLE 5 AVERAGE PHOSPHATE SPECTRUM OF THE FLEURUS SLUDGE SPREAD AT GEMBLOUX (RESULTS EXPRESSED IN mg P 0/100 g DRY MATTER, IN % OF TOTAL P AND IN kg P 2 0 5 /ha). Fractions mg P 0 / 1 0 0 g D M % TP kg P 2 0 5 / h a 0 1 002 12.59 275 A 3 430 43.08 950 B 156 1.96 44 C 1 895 23.80 523 Org. 1 478 18.56 396 total 7 961 100.00 2 188

-406-

The soil was sampled at two levels: 0 to 0.15 m and 0.15 to 0.25 m. These levels were chosen with respect to the depth of ploughing for the study of mineralisation of organic N (0 to 0.15 m: area of ploughing; 0.15 to 0.25: limit for the ploughing depth). As a result of observations from the previous two fields, which had proved difficult to interpret, the samples were analysed for total P and for forms of P. Sampling was carried out by means of 25 core samples per block or per plot, using a manual borer. Sampling was carried out before the sludge was ploughed in (May 1979) at the rate of one sample per block (2 depths) and repeated 3 times during the cultivation season at a rate of one sample per plot (2 depths). The last samples were taken during the harvest (Oct. 19 79). DISCUSSION OF RESULTS The results for the average values obtained for the 4 repetitions of each sampling are shown in Table 6. Statistical analysis using test 't' for the comparison of averages shows the existence of a significant increase in total P content in layer 0 to 0.15, an increase which also appears in fractions 0 and A. During the course of the second sampling, fraction B shows a significant decrease between the two treatments, whilst there is an extremely significant increase in the organic fraction content. Occasionally, significant differences between the treated and the control plots are noticeable in the deep layer. Nonetheless, the significant differences which have emerged for total P do not make it possible to trace the additional P which is in the region of 2188 kg P ? 0 /ha. Indeed,

-407-

TABLE 6 SOIL CONTENT OF TOTAL P AND THE VARIOUS FORMS OF P (RESULTS EXPRESSED IN mg P 2 0 5 /100 g ) .

Fractions Sampling
.-i 0 H 4J C 0

in CO i - l

10

12

36

40

41

46

62

67

69

65

o
M-l

Sur (0 -

ni O

u
E

8
+1
0

21

**

22

**

26

36

*
51 53

* 62 * 62

58

63

65

m)'

CM

C 0

35

37

36

40

63

63

66

63

a i
a)
H

u s

o
1 2 3 4

8
+1

10

11

35

38

42

43

63

56

64

62

= sampling carried out on the 18/04/79, per block (prior to the spreading of sludge) = " " 18/06/79, per plot = " " " " " 08/08/79, " = " " 04/10/79, "

* : test t' significant at level of a = 0.05 between control and 300 m .

**.

"

"

"

"

"

" a = o.oi

"

"

"

"

TABLE 6 CONTINUED

Fractions Sampling
0
>)

C 1 2 3 4 1 2

org. 3 4

P total 1 2 3 4

a) "a o m
m ,-J iw .

c 0 u n

57

'61

61

61

89

87

96

91

250

265

278

277

C O o

a o o
m
+i .-1

57

60

62

61

89

100

107

92

250

2 9 6 * 308* 307*

0 c
0

59

61

59

57

93

88

88

92

255

256

256

261

. e in iJ C N
&

a?
in

s
+1

6 O

59

57

59

56

93

94

101

94

255

256

278

263

1 2 3 4

=O s a m p l i n g carried out on the 18/04/79, per block (prior to the spreading of sludge) ii = 18/06/'$), per plot. ii = 08/08/79, " I = 04/10/79, " test
II II

* : **. ***

f
II It

significant at level a = 0.05 between control and 300 m

II II II ~y _ fl

/-|-|

II

II

II

II

"

a = o.ooi

"

"

"

in both layers studied the contents under observation show a heavy enrichment which amounts to 613 kg P-O^/ha. There is thus a loss of 1 575 kg P-Or/ha in the first 25 cm of the soil. This loss cannot be explained by plant requirements, which represent about 30 kg of P-0[-, both in the treated and in the control plot, for the leaves, shuck and stems of maize, whilst the core samples can be estimated at 60 kg. CONCLUSION We were unable to find the quantities of P added in the three fields, even when the samples were taken from a depth of 50 cm. This implies either a loss of P through leaching towards the deeper layers, or an overestimation of the P content in the sludge analysed, due to the analytical method employed. The results have enabled us to point to a few significant facts regarding the evolution of the various fractions, mainly at Gembloux, where a systematic increase in fractions 0 and A over a period of time was observed in the surface layer. and about 20% of the initial fraction A content. REFERENCES Avril, P. 1978. Legende de la carte des sols de Belgique, Service de la Science du Sol. Faculte des Sciences Agronomiques de l'Etat, Gembloux, Belgique. Cooke, G.W. 1973. The possibilities of polluting soils by fertilisers and the way they are used. Bulletin de Recherches Agronomiques de Gembloux. Volume extraordinaire, 561-583. Cottenie, A. 1972. Effect of soil enrichment with mineral elements and fertilisers on surface water and plants. Soils Bulletin, 16, F.A.O. 34 3-356. Hanotiaux, G. et al. 1980. P content and the forms of P in sewage from Wallonian water purification plants. Commission of the European Communities, Environment and Raw Materials Research Programmes. Seminar on Phosphorus in Sewage Sludge and Animal Waste Slurries.
-410-

These

increases reached about 100% of the initial fraction 0 content

Kolenbrander, G.J. 1972. 305-327. Vollenweider, R.A. 1968.

E u t r o p h i c a t i o n from a g r i c u l t u r e with s p e c i a l S o i l s B u l l e t i n , 16, F.A.O.

r e f e r e n c e t o f e r t i l i s e r s and animal w a s t e .

Les bases s c i e n t i f i q u e s de l ' e u t r o p h i s a t i o n des O.C.D.E.

l a c s e t des eaux courantes sous 1 ' a s p e c t p a r t i c u l i e r du Phosphore e t de 1'Azote comme f a c t e u r s de l ' e u t r o p h i s a t i o n .

DISCUSSION E.G. Coker (UK) I wonder whether the reason why you have not found all the phosphorus that you think is there is partly due to the mixing with the soil and the irregularity of the distribution within the soil in the period after application? I see that this was put on with a muck spreader which may have caused problems with random sampling. We had an experience rather similar to this during the winter before last when we applied heavy applications of a 10% sludge to land; at the first sampling, a few months after application, we only succeeded in recovering about 50% of selected indicated metals. Twelve months later when the material had become better incorporated with the soil a resampling showed that it was all there. L. Barideau (Belgium) I will try to answer the question. This may be true in the case of the trial at Gembloux where we used a muck spreader with injectors. In the other cases the sludges were spread on the surface of the soil and incorporated later by tillage. One of the trials is now two years old so I think the question still remains.

411

FINAL

SESSION

Chairman: A. C o t t e n i e

413-

FINAL DISCUSSION A. Cottenie (Belgium) We have now come to the end of the communications and we have some time left for a general discussion. I would like to start this by making one or two comments and posing some questions. Is it now possible for us to generalise some of our observations? I think perhaps we can make some general conclusions. What can we extrapolate from all our observations? Are there points of contradiction and are there unanswered questions? I think there is some contradiction when we see that in a very general way leaching does not seem to be a major point of concern at this moment but a significant amount of phosphate seems to remain soluble to enrich the soil solution. There is a movement in the soil profile of phosphate but leaching is not observed. Is that a contradiction or not? Shall we reach a breakthrough point because it is a very general statement, that using slurry, using sludges, we are enriching our soil? There is a general increase in the level of phosphorus content in all the soils we are treating and in some conditions the treatment seems to be more a 'dumping' than a dressing already. So the question we must answer is what is the storage capacity of the soils, or of the surface layer of the soils, before we eventually reach a breakthrough point - or shall we never reach that? I think that is the question to be discussed and it is our responsibility. Another point is the influence on crop quality. With regard to the phosphorus content in fodder crops there has been some disagreement but this might be due, as has been suggested already, to the different stages of development. With a fodder crop like grass, the stage of development of the plant may have a big influence on the phosphorus content. There is an evolution in function of time.

415-

There is another point which remains an open question. When we make balances they never seem to be equilibrated. We know the input; if we total all that we find after analysis of crops, water and soil, then we are left with a balance which is not in equilibrium. The question has been raised several times - where is the remainder? So, these are the questions still to be answered or discussed. I open the discussion. A.E. Johnston (UK) I believe it was Lawes and Gilbert who, after their early analyses in the 1870s, made the statement that if you look at the composition of a plant you invariably find that the reproductive part will have a composition which is very difficult to change. In other words, the percentage of nutrients in grain or seeds is usually remarkably constant over a wide range of applied treatments to nutrients. It is in the composition of the vegetative part of the plant that you can get extreme changes. This was shown in many of their very early experiments and, of course, everybody has got a lot of data which has gone on to show this since. However, when we look at phosphate in any part of the plant we must remember that we are looking at very small amounts. Some of the grain percentages of P that we looked at yesterday changed from 0.28% to 0.32%. This is a change of 0.04 on 0.28 which is getting towards 10%. If you can change the yield of a plant by 10%, as an agriculturist you reckon you have done very well. I think these changes of 10% in terms of nutrient composition are probably as meaningful as a 10% change in yield. You have to consider the percentage change as well as the absolute values. A. Cottenie Yes, and we .must keep in mind that the uptake pattern of the different nutrient elements is very different. You can
-416-

have a big increase for some elements - for potassium and chloride, for example - and very small increases in function of doses for phosphorus and calcium. But certainly, 10% is always meaningful.
H . Tunney (Ire land)

When you speak about breakthrough levels for soils, I think it is interesting that we have already seen this morning one soil that has reached its breakthrough - the peat soil. So there can be very big differences between soils. On a mineral soil, perhaps on average agricultural soil, where you can continue to add a lot of lime and where the build-up of phosphorus will be in the form of calcium phosphate, you can add very large quantities. So perhaps you eventually reach a stage, in the very extreme situation, of having a soil which is 50% calcium phosphate. You might be losing less phosphorus from that soil than you would from the peat soil. So it is fairly complex. A. Cottenie Soil conditions are extremely important in reaching such points. I should mention a study which was made in our laboratory by one of the assistants for his doctorate. He took Nigerian soils and added amounts of phosphorus as fertiliser in order to observe at which stage it was possible to have a response from the crop. These were ferritic soils. Quantities of at least 3 000 kg of P2C>5 were needed before there was the slightest reaction from the plants. So these were absolute fixing phosphorus soils. But the question remains, must we now aim to increase the phosphate fixing power of our soils because we have so much slurry and sludge? E.G. Coker (UK) While we have been very preoccupied with the problems of accumulation of large quantities of phosphate, I do not think
-417-

we should lose sight of the response of crops to phosphate at low levels of application of slurries and sewage sludges. Inevitably, there are many areas where large quantities must be put on land, of necessity. But where there is sufficient room for manoeuvre it seems to me worthwhile moving towards a situation where these things are put on soil at rates which are more compatible with crop utilisation. Dr. Furrer has referred to the kind of rates. This means putting such materials on land at rates which are rather expensive if small quantities of phosphate are to be put on frequently. It would, therefore, be helpful if we knew more about the kind of quantities of phosphate put on which would cover a period of, say, five or six years at one go. It would make a more economic application and would establish whether the phosphates remain available and useful to plants over that period. R. Unwin (UK) I presume Dr. Coker is thinking more in terms of sewage sludge applications than those of animal slurries. But, again, we must not lose sight of animal slurries. Five year applications to take care of phosphate levels will give excessive amounts of nitrogen and most certainly excessive amounts of potash in terms of manuring of forage grassland crops in particular, A. Cottenie Then there is the question of the ratios, N : P as well as C : N. R.E. White (UK) I would like to take up the point of the storage capacity of the soil for phosphate. However, I don't think many people have actually measured storage capacity in the sense that soil chemists think of it. We have heard about fractionation procedures for phosphate and I think the analytical difficulties there are so great as to make the Chang and Jackson approach.

-418-

however modified, worthless. Total phosphorus is a reasonable measure but the problem arises when we want to look at storage capacity and the amount of phosphate which might be in solution. Here I would suggest that we really ought to look at adsorption/ desorption methods, studying the extent to which the soil solids can buffer the soil solution against either the addition of large amounts of phosphate or the removal of phosphate. It may be that we will need to modify the technique to develop column experiments in laboratories in which we look at adsorption in relation to flow rate - or something like that. But I would suggest that we think quite strongly about this because there may be a lot of questions that need to be answered, which could be answered in this way - for example, the difference between farmyard manure and sewage sludge may be related to the different effect that these materials have on the adsorption capacity of the soils. A. Cottenie When you determined the ratios, did you always consider total N and total P? You prefer total phosphorus rather than separating fractions? R.E. White Yes, when I was looking at organic materials I looked at total P and total carbon. However, there is plenty of evidence to show that with most of these materials, the bulk of the phosphorus, for example, is in the inorganic form. H. Vetter (FRG) Mr. Chairman, you pointed out that we have leaching on the peat soils but not on the mineral soils. I would repeat that we found on soils with a high humus content, a higher amount of P in the groundwater - not a difference after the application of varying amounts of slurry. I would expect that if we do experiments over a long period we will also find higher P leaching on mineral soils with a high humus content. From this point of view I agree that it is important to make further

419-

studies to establish the storage capacity, or the content of P at which leaching begins. There are regions with a high stocking density and I do not believe that farmers in such regions can continue to apply the amounts they are doing at the moment indefinitely. A. Cottenie Yes, and in the meantime the production of sludges is increasing in many countries. Here in Western Europe we are all constructing more and more water purification plants. H. Kick (FRG) I think we should also discuss the policy which we should pursue. You mentioned 'dumping' but a lot of the work presented here has been aimed at avoiding dumping. The object must be to utilise all this material as fertiliser, not just to get rid of it. The other point is that we cannot only consider phosphorus levels, we must also take into account nitrogen, potassium, etc. A. Cottenie We have to keep in mind that sludge is especially rich in phosphorus, slurry contains much more nitrogen. But we should never accept dumping. Mr. Johnston spoke about his experiments in which the application of sludge stopped 20 years ago. Can we just assume that the quality of that sludge was the same as the ones we produce now? I don't think so. It seems clear that the phosphorus content of the actual sludges is much higher than it was 20 years ago, due to the use of all sorts of bleaching and cleaning products. A.E. Johnston That is probably true but since we stopped the experiments we have had no more samples from that particular works. I think we could probably find out; it is a very large works on the outskirts of London. It might well be possible to find the
-420-

current phosphate content of sludges that are produced. A. Cottenie The other factor is whether, in the future, the sludges will continue to be so rich in phosphorus because there is a general industrial concern to decrease the content of phosphorus and phosphorus compounds in all cleaning and bleaching materials. In the chemical industry people are looking for alternative products at the present time. We might be faced with problems with other elements in the future. H. Kttntze (FRG) Coming back to Professor Vetter's comments, between the increasing phosphorus content in the upper layer of the soil, and the leachate of phosphate, there is the enrichment of the subsoil. It seems to me an optimistic sign that we can enrich the subsoil with phosphorus because as a result of the previous application only the fertilised nitrogen and the fertilised potassium leached and the phosphoric acid was enriched. In my opinion it is a good way of improving soil fertility if we can enrich the subsoil to an optimum level. A. Cottenie That is a very different point of view now. During recent years we have always heard that the enrichment of the soil with phosphorus and other elements should be limited. Dr. Dam Kofoed wrote a paper in which he recommended using up these stored quantities of phosphorus in our soils before adding more. But you are recommending to go on, and to enrich also the subsoil. I don't know if we can agree on this point. A.E. Johnston We have just had the results from an experiment which we have now had going for six years where we have, in fact, enriched subsoils at the 23 - 46 cm depth with both phosphate and potassium at Rothamsted. Over a period of seven years this enrichment has shown very considerable benefit to crop yield of potatoes, barley,
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sugar beet and winter wheat. The major problem has been to get phosphate and potassium into the subsoil. In the original experiment this was done by hand but very recently our colleagues at Wye College have produced a machine which will, in fact, cultivate the subsoil satisfactorily. That machine has been tested and we are now in our first major year and we are hoping to get some results in September. But there have been very considerable benefits from subsoil enrichment. A. Cottenie So this is a positive point, we should recommend much deeper ploughing than we have done until now. A.E. Johnston The danger with very much deeper ploughing is that you dilute the organic matter content; E.W. Russell's early experiments show that that is a very considerable drawback. H. Kuntze I arrived at this conclusion from the following idea: the most fertile soils we have in our northern region in Germany, and in the Netherlands too, are the so-called black ash soils. This is a special kind of soil built up by farmyard manure composted in the stables centuries ago. A. Cottenie Of course we must bear in mind the guidelines of the European Commission for the quality of surface water. This is very strictly limited to 0.4 and 0.7 mg/1 of P20c f r soil and surface water. This is official legislation in all our countries at the moment. So we must ensure that agriculture is not responsible for too high an increase in these levels - which are quite low anyhow. H. Kick Why is there not a distinction between surface water, in
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rivers or lakes, and groundwater? If you are talking about a source of drinking water then the situation is very different. A. Cottenie The regulations are very strict. There are two classes and it is for every type of soil water - " . . . . which might be considered as starting water for preparing drinking water..." That is the official legislation in all our countries. H. Kick I do not understand why, why is the high P content in drinking water important? A. Cottenie This is a question of public health, and so on. H. Kick I still don't see why the same regulations should apply in the case of groundwater. J.H.A.M. Steenvoorden (Netherlands)

Groundwater infiltrates can reach surface waters because of the hydrological regime. I think this applies in many countries. A. Cottenie In my country we have drinking water being pumped from 80 m depth. Of 16 of these wells, only three are in accordance with the legislation at the moment, due to pollution, mostly with nitrogen but in one or two cases due to a too high content of phosphorus. This is in an industrial region and there is a fertiliser factory; the effluents from there are reaching the groundwater. So some of these wells cannot be used because the water, even though it is pumped from a depth of 80 m, does not meet the legal requirements. The question is being asked now

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whether it is the factory or agriculture which is causing the so-called pollution. H. Kick We have many villages which have water, not from the groundwater but from the surface water, that is also a problem. A. Cottenie Before we close this session would Dr. Catroux or Mr. Hucker like to make any comments? T.W.G. Hucker (UK) I think everyone here knows the division between Dr. Catroux and myself - Dr. Catroux looks after the manurial value, the good things of sludge, and I try to look after the bad things. I started the week with the idea that everyone was looking for phosphorus and that Dr. Catroux would have no difficulty in determining its value. However, as the week has gone on I have become more worried, especially in the last two or three minutes. Perhaps Working Group 5 has got to take a little more interest in phosphorus; it will finish up with Dr. Catroux but we have got to see that the good and bad effects are taken into account. On the other hand, having worked with the water industry I have always thought, like Dr. Kick, that eutrophication resulted from phosphorus and nitrogen and that provided you made sure the sources did not have eutrophication trouble, you were all right with your drinking water. I am sorry to hear about the Belgian trouble but that is not our experience in the UK. Finally, please don't blame sewage sludge for all the troubles because in England all the sewage sludge would only provide 5% of the agricultural demand for phosphorus. We can get rid of our sewage sludge to farmers provided the transport costs are covered. A. Cottenie

Before giving the floor t o Dr. de Haan for the f i n a l words

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I would like to thank all of you for the pleasure of this morning, to thank all our speakers who have once again brought interesting papers and discussion subjects, and I thank as well our colleagues who have taken part in the discussions. I would also like to thank our hosts here in Groningen, Dr. Sluijsmans, the Director of the Institute for Soil Fertility who received us, and his staff; also Dr. de Haan who has done everything he can to make us comfortable here. I now give him the floor for the final words.

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CLOSING REMARKS
S. de Haan (Netherlands)

Ladies and gentlemen, I prepared these remarks this morning before the final sessions so perhaps they are not quite up to date. Nevertheless, I will read them to you. We have now come to the conclusion of our seminar and I have been asked to summarise what we have done in a few sentences. Of course, at this stage, that is possible only from a very personal point of view which is a point of view more of a farmer than of a scientist. I am not a politician; I am not a water specialist. We came together here to evaluate phosphorus in sewage sludge and animal slurries as plant nutrients and as a possible source of ground and surface water pollution in connection with eutrophication. Generally speaking, the availability of phosphorus for plants and mobility in soil is very low. However, sewage sludge and also animal waste manure may be regarded these days as waste products for which agricultural land is the cheapest dump, but then a certain risk of water pollution cannot be excluded. The risk of excessive P concentration in crops seems to be less. There was even doubt as to whether 'luxury' consumption of P exists. However, we should keep in mind that sewage sludge, and especially animal slurries are primarily nitrogen fertilisers. In my opinion, the phosphorus effect of sewage sludge and animal slurries can only be studied if the effect of nitrogen and other elements is eliminated or compensated for. In comparison with superphosphate, for example, there is no indication of a lower mobility or availability of phosphorus in animal slurries. Some organic compounds could be more mobile but this might also be a question of transport by water, which is the main component of slurries, through large pores or cracks in the soil.
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Availability and mobility of phosphorus in sewage sludge could be lower when contents of lime, iron, aluminium or other heavy metals are high. This might especially be the case if iron and aluminium salts are used for P removal. Normally, the solubility of these elements in soils is very low but this is not a rule without exception. I was born in a region where sand, clay and peat soils meet each other. The groundwater level was rather high and up until World War II, and even later, we pumped the water we used from a depth of, say, 2 m. If the water was left in buckets for half an hour a layer of iron had settled on the bottom. The water in the ditches was red from iron. Effectivity of superphosphate in these soils was very low. In my opinion, excess iron in sewage sludge may have the same effect, although it may depend on the type of soil to which sewage sludge is applied whether or not this effect appears. In Working Party 4, I have been asked to summarise the data we have had presented in this seminar about phosphorus in sewage sludge, and to report on this at the conference in Vienna in October, in co-operation with Dr. Gupta a : j d Dr. Hani of the Swiss Federal Institute for Environmental Studies. In my opinion, a similar report should be brought out for phosphorus in animal slurries. Perhaps these reports could be added to the Proceedings of this meeting if we do not work too slowly and if Janssen Services and the' EEC do not work too fasti Ladies and gentlemen, these remarks have been made with regard to the technical aspect of our meeting, but of course, our meeting also had a social aspect. Again, I will give my personal impression of this aspect. I was happy to meet again with old friends and make contact with people previously unknown to me. I thank you all for the way in which you met me and I hope you will all remember this meeting as a pleasant one. I wish you a safe journey home and I hope you will find your families happy and
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well. To those who are combining the seminar with holidays, I wish you a pleasant holiday. Thank you. A. Cottenie (Belgium) Thank you very much Dr de Haan. Before we leave I would like to acknowledge the role of Mr. L'Hermite and Mr. Dehandtschutter, the administrators of the CEC who made our meeting here possible. Thank you all, and goodbye.

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LIST OF PARTICIPANTS Dr. M. Ahtiainen North Karelian Water District Office PO Box 69 80101 Joensvu 10 FINLAND Groupe d'etude des Boues Faculte des Sciences Agronomiques B-5800 Gembloux BELGIUM Swedish Environmental Protection Board Box 1302 S-17125 Solna SWEDEN Ministere de 1'Agriculture INRA Laboratoire de Microbiologie des Sols 7 rue Sully B.V.1540 21034-Dijon Cedex FRANCE Institute of Agriculture and Microbiology University of Naples 80055-Portici ITALY Water Research Centre Elder Way Stevenage Hertfordshire UK Faculty of Agronomy State University of Ghent Coupure Links 53 3 B-9000 Ghent BELGIUM Askov Experimental Station 6600 Vejen DENMARK Landbouwscheikunde De Dreyen 3 Wageningen THE NETHERLANDS Institute for Soil Fertility Oosterweg 92 Haren (Gr) THE NETHERLANDS -431

Dr. L. Barideau

Dr. S. Berglund

Dr. G. Catroux

Prof. S. Coppola

Dr. E.G. Coker

Prof. A. Cottenie

Dr. A. Dam Kofoed

Dr. F.A.M. de Haan

Dr. S. de Haan

Mr.

Dehandtschutter

Commission of the European C ommunities DG VI 200 rue de la Loi B-1049 Brussels BELGIUM Centre de Recherches Agronomique de l'Etat Station de Chimie et de Physiques Agricoles 5800-Gembloux BELGIUM Institute of Waste Disposal Natriumweg 7 Post Box 184 Amersfoort THE NETHERLANDS The Agricultural Institute Johnstown Castle Research Centre Wexford IRELAND Swiss Federal Research Station for Agricultural Chemistry and Hygiene of the Environment 3097-Liebefeld (BE) SWITZERLAND Institute for Soil Fertility Oosterweg 92 Haren (Gr) THE NETHERLANDS CNR Institute for Soil C hemistry Via Corridoni 78 56100-Pisa ITALY Swiss Federal Research Station for Agricultural Chemistry and Hygiene of the Environment 3097-Liebefeld (BE) SWITZERLAND Institut fur Bolanik Universitat fur Bodenkultur Gregor Mendelstrasse 33 A-1180 Vienna AUSTRIA Swiss Federal Research Station for Agricultural Chemistry and Hygiene of the Environment 3097-Liebefeld (BE) SWITZERLAND

Dr. J.P. Destain

Dr. L.E. Duvoomt van Engers

Dr. G.A. Fleming

Dr. O.J. Furrer

Dr. R. Gerritse

Dr. G. Guidi

Dr. S. Gupta

Dr. G. Halbwachs

Dr. H. Hani

432-

Mr. T.W.G. Hucker

Department of the Environment 2 Marsham Street London SW1 UK Rothamsted Experimental Station Harpenden Hertfordshire AL5 23Q UK Agrikulturchemisches Institut der Universitat Bonn D-5300 Bonn FEDERAL REPUBLIC OF GERMANY Agricultural Research Centre MTTK PL 42 00131-Helsinki FINLAND Institut fur Bodenkultur Fr. Missler Strasse 46/50 2800-Bremen FEDERAL REPUBLIC OF GERMANY Askov Experimental Station 6600 Vejen DENMARK Commission of the European Communities DG XII 200 rue de la Loi B-1049 Brussels BELGIUM Department of Agriculture (Northern Ireland) Newforge Lane Belfast BT9 5PX UK ENSAIA 38 rue Sainte Catherine 54000 Nancy FRANCE The Agricultural Institute Johnstown Castle Research Centre Wexford IRELAND INRA 3 3140 Pont de la Maye Bordeaux FRANCE

Dr. A.E. Johnston

Dr. H. Kick

Dr. I. Koskela

Prof. Dr. H. Kuntze

Dr. K.E. Larsen

Dr. P. L'Hermite

Dr. J.S.V. McAllister

Dr. J.L. Morel

Dr. E.G. O'Riordan

Dr. B. Pommel

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Mrs. M.J. Robins

Janssen Services 14 The Quay Lower Thames Street London EC3R 6BU UK Faculte des Sciences Agronomiques de l'Etat 58000-Gembloux BELGIUM Federal Agricultural Research Centre Bundesallee 50 D-3 300 Braunschweig FEDERAL REPUBLIC OF GERMANY Spelderholt Institute for Poultry Research Beekbergen THE NETHERLANDS Institute for Land and Water Management Research (ICW) Wageningen THE NETHERLANDS LUFA Mars-la-Tour Strasse 4 2900 Oldenburg FEDERAL REPUBLIC OF GERMANY Ministry for Public Health and Environmental Protection Post Box 439 2260 AK Leidschendam THE NETHERLANDS Institut fur Wasserwirtschaft Universitat fur Bodenkultur Gregor Mendelstrasse 33 A-1180 Vienna Austria Bayerische Landesanstalt fur Bodenkultur und Pflanzenbau Vottinger Strasse 38 8050-Freising FEDERAL REPUBLIC OF GERMANY Experimental Station for Arable Crops and Outdoor Vegetables Edelhertweg 1 Lelystad THE NETHERLANDS The Agricultural Institute Johnstown Castle Research Centre Wexford IRELAND -434-

Dr. M. Rocher

Dr. D. Sauerbeck

Dr. P.CM. Simons

Dr. J.H. Steenvoorden

Dr. G. Steffens

Dr. J. Strybis

Dr. H. Supersperg

Dr. A. Suss

Dr. H. Titulaer

Dr. H. Tunney

Dr.

Unwin

MAFF Horseferry Road London SW1 UK Agricultural University Wageningen De Dreyen 3 Wageningen THE NETHERLANDS LUFA Mars-la-Strasse 4 2900 Oldenburg FEDERAL REPUBLIC OF GERMANY The Agricultural University Box 48 1432 AS-NLH NORWAY Government Agricultural Wastewater Service Kemperbergerweg 67 Arnhem THE NETHERLANDS Wastewater Technology Centre PO Box 5050 Burlington Ontario L7R 4A6 CANADA MAFF Woodthorne, Wolverhampton West Midlands UK Department of Agricultural Science University of Oxford Parks Road Oxford 0X1 3PF UK

Dr. W.H. van Riemsdijk

Prof. Dr. H. Vetter

Dr. E. Vigerust

Ir. J.H. Voorburg

Dr. M. Webber

Dr. J.H. Williams

Dr. R.E. White

435

INDEX of SUBJECTS Accumulation and leaching of Phosphorous and 235-240 -Transport of 231-234 Agriculture Application 191-205 Agricultural Development and Advisory Service (ADAS) U.K. 334, 337, 342 Agriculture University Wageningen 77, 83 Air-dried Sewage Sludges Experiments 245-247 Algal Growth 6-8 Askov Experimental Station Denmark 207, 212-218, 220, 223-225 Availability of Phosphorus in Sewage Sludge 177-188 -Abstract 177 -Characteristics Tables 181, 182 -Discussion 189, 190

Chang & Jackson Fractionation Method 177-179, 256, 374, 376 Computer Simulation of P Mobility 362-365 Consumption of Mixed Feeds - Netherlands Table I 120-122 Consumption of Organic Manure in Denmark 208 -Tables 209 Crops - Effect of Phosphorus 241-253 - Carbon/Phosphorus ratios 28-42, 52
-437-

-Discussion 45-46 -Quality of 13, 72, 75, 195 Drainage Water - Phosphorus Effect 241-253 Dutch Commodity Board for Animal Nutrition 129-131

Eutrophication - in The Great Lakes 5-20, 22 Evolution of Soil Kinetic Parameters 170-172 Experimental Fields for Evolution of P Fractions in Sewage 400-410 -at Beuzet 401-403 -at Fleurus 402, 404 -at Gembloux 405-407, 410

Farmyard Manure (FYM) and Phosphorus Accumulation 209, 211-213, 273-286, 298, 334 Fertiliser from Sewage Sludge 22, 62, 72, 97, 149-162, 172, 192 Finland - Phosphorus in Sewage Sludge 109-118 Fractionation of Phosphates, -Tables 257, 259 Freshwater Phytoplankton Communities 6-7

General Aspects - Phosphorus Cycle in Soils 3-5 Global Phosphorus Cycle 23, 24, 26 Great Lakes - Water 5-20 Quality -Eutrophication of 5 -Water Quality Agreement 7, 9, 10

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Guelph - University of

12

Herbage Composition -Phosphorus ratio in

335-337 336, 337

IHP Accumulation 352, 353 Influence of Nutrational and Physiological -Factors - Phosphorus in Animal Manures 119 -Abstract 119 -Calcium in the Diet 124 -Phosphorus in the Diet 121, 122 -Discussion 132, 133 Institute for Soil Fertility, Haren, Netherlands 241, 347 Isotopic Kinetics measuring Method 163-175 -Abstract 163 -Conclusions 173

Kanteerd' Soil Kick-Brauckmann Pots Kinetics of Phosphate Binding Kjeldahl Nitrogen (TKN) Loadings

50-52 19 3, 194 48-50, 55, 57 12

List of Participants 431-437 Livestock Effluent - Effects from -Intensive Dressings on Phosphorus in Soil 371-380 Long term Phosphate -Binding 47-87 -Abstract 47

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Lough Neagh (N.Ireland) -Phosphorus Input

393-395

Metal Concentrations - Sludge treated Soils -Fig. 2 13 -Metal concentrations -Metal content in sludge phosphorus 37-148 -Maximum permissible in drinking water - Canada 17, 18 Michaelis-Menten Rate Constants -(Table 5) 355 Ministry of Agriculture, Fisheries and Food (MAFF) U.K. 334, 335

Organic Fertilisers Almelo & Alkmaar examples -Discussion

250-252

253, 254

Participants - List of Phosphorus - Effect of -Accumulation in Sandy Loam -Accumulation and transport -After land spreading -Animal Manure and Sludge -Balance after application -In Crops & Drainage water -Farmyard Manure (FYM)

431-437

273-286

235-253 207-229 255-272 241-253 273-286

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-In Sewage Sludge & Behaviour in Soils 291-308 Phosphorus - in relation to -Accumulation in Soil Profiles 309-328 -Analysis in Soils 71-88 -Applications in Agriculture 191-202 -Content in Animal Manures 119-132 -Evolution in Sewage Sludge and 399-411 -Large Slurry Applications 333-345 -Long term Binding in Soils 47-69 -Losses from Animal Manures 328 -Mobility in Pig Slurry in Soils 347-367 -Pathways in Soil 21-46 -Problems in Disposal of Slurry 383-397 -Removal by Precipitation 10 -In Sludge from Finland 109-118 -In Sludge Metal Content 137-148 -In Sludge from Swiss Plants 91-98 -In Wallonian Purification 99-108 -Soil Application -Table 2 of Concentrations 15 (Great Lakes) Fig. 3 -Water Quality 5-20 -In Wastes 91-108 Phosphate -Availability Fractions 177-189 -as Fertiliser 149-162, 195-197

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in Mobility Soil Processing

163175

RosinskyZeldovic Equation Rotation Table Field Experiment 1 Parabraunerde'

58

263265

Sewage Sludge as a Phosphate Fertiliser 149, 305, 306 Mean relative Values table 157 Simultaneous Precipitation of Phosphorus 109, 110 in Helsinki 110 Sludge Production Great Lakes Table I 11 Soil Fixation 350352 Soils P Status Charac teristics 7679, 81 Swiss Sewage Treatment Plants 9198 Abstract 91 Discussion 98

Trophic Status of Great Lakes, fig. I

11

University of Guelph

12

Wallonian Water Purification Plants 99108

442-

-Abstract -Introduction Wastes - Phosphorus in -Abstract -Experiment Tables -Discussion Wastewater Technology Centre, Ontario Woburn Market Garden Experiment

99 100, 101 100, 101, 136 137 141 147 12 274-276, 278, 279, 281-284, 296, 297

443-